Nano-particulate blends with fully-neutralized ionomeric polymers for golf ball layers

ABSTRACT

A golf ball comprising a core, an intermediate layer, and a cover. The core, which has a compression of 100 or less and a diameter of between about 1.00 inches and about 1.64 inches, is formed from a first polymer including an acid group fully-neutralized by a salt of an organic acid, a cation source, or a suitable base of the organic acid; and a nano-material having an average particle size of 100 nm or less, present in an amount sufficient to adjust at least one material property of the first polymer by 5% to 50% when compared to the material property of the first polymer comprising a material identical to the nano-material but having an average particle size greater than 1000 nm. The intermediate layer is formed from a second polymer comprising an acid group fully-neutralized by a salt of an organic acid, a cation source, or a suitable base of the organic acid.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation-in-part of U.S. application Ser. No.10/037,987, filed Jan. 4, 2002 now U.S. Pat. No. 6,919,395.

FIELD OF THE INVENTION

This invention relates generally to compositions for golf ball cores,intermediate layers, and covers and, in particular, compositionscomprising fully-neutralized ionomers and a variety of nano-materialsfor improving the physical and mechanical properties and/or performanceof virgin fully-neutralized ionomeric materials.

BACKGROUND

Golf balls have a variety of constructions. Solid golf balls includeone-piece, two-piece (i.e., solid core and a cover), and multi-layer(i.e., solid core of a center and one or more layers and a cover of oneor more layers) golf balls. Wound golf balls typically include a solid,hollow, or fluid-filled center, surrounded by a tensioned elastomericmaterial, and a cover. While solid golf balls now dominate themarketplace because of their distance, lower cost, and durability,manufacturers are constantly trying to improve the “feel” of solid ballsin an attempt to make it more like that associated with a woundconstruction.

By the materials used for golf ball construction, manufacturers can varya wide range of playing characteristics, such as compression, velocity,“feel,” and spin, each of which can be optimized for various playingabilities. In particular, a variety of core and cover layer(s)constructions and compositions have been investigated, such as polymericcompositions and blends, including polybutadiene rubbers, polyurethanes,and ionomers. These ‘conventional’ materials, however, have inherentlimitations in their properties.

It is now believed that blending nano-materials with conventionalmaterials can improve the properties of the virgin material. It is alsobelieved that forming golf ball layers with conventional materials in‘nano’ sizes (≦100 nm) can provide improved properties compared to thatof the same ‘larger’ material. The properties that can be improvedinclude, but are not limited to, density, dimensional stability,stiffness, abrasion resistance, moisture transmission, and resiliency.Nanomaterials are unique because of their size and shape, and becausethey can be selectively modified by chemical or other sources at anatomic or molecular level. These nanomaterials, therefore, provide noveland sometimes unusual material properties (even at lower loadinglevels), such as increased modulus (in some cases even lower hardness),elongation at break, optical property, barrier to moisture, abrasionresistance, low hysteresis, and surface appearance, especially comparedto identical materials of conventional (larger) size. These uniqueproperties may be utilized for golf ball construction in mannerspreviously not available.

There remains a need, therefore, for improved golf ball layer materials,in particular, core and intermediate layer materials formed fromfully-neutralized ionomeric polymers blended with nano-particulates.These blends may further be a suitable substitution forpolybutadiene-based core materials so commonly used in convention golfball cores.

SUMMARY OF THE INVENTION

The present invention is directed to a golf ball having a core, anintermediate layer, and a cover. The core is formed from a first polymercomprising an acid group fully-neutralized by a salt of an organic acid,a cation source, or a suitable base of the organic acid, and anano-material having an average particle size of 100 nm or less, presentin an amount sufficient to adjust at least one material property of thefirst polymer by 5% to 50% when compared to the material property of thefirst polymer comprising a material identical to the nano-material buthaving an average particle size greater than 1000 nm. The intermediatelayer, which is disposed between the core and the cover layer, is formedfrom a second polymer including an acid group fully-neutralized by asalt of an organic acid, a cation source, or a suitable base of theorganic acid. The core typically has a compression of 120 or less and adiameter of between about 1.00 inches and about 1.64 inches.

The material property is selected from the group consisting of density,hardness, moment of inertia, flexural modulus, stiffness modulus,abrasion resistance, heat resistance, impact resistance, water vaportransmission rate, and resilience.

The material property of the first polymer is flexural modulus at least10% to 50% greater than when compared to the flexural modulus of thepolymer comprising a material identical to the nano-material and havingan average particle size greater than 1000 nm. the material property ofthe first polymer is hardness at least 5% to 25% greater than whencompared to the hardness of the polymer comprising a material identicalto the nano-material, the material having an average particle sizegreater than 1000 nm.

The cover layer includes a polymer selected from the group consisting ofionomeric copolymers and terpolymers, ionomer precursors,thermoplastics, thermoplastic elastomers, polybutadiene rubber, balata,grafted metallocene-catalyzed polymers, non-graftedmetallocene-catalyzed polymers, single-site polymers, high-crystallineacid polymers and their ionomers, rosin-modified ionomers, bimodalionomers, cationic ionomers, amonic ionomers, polyurethanes, andpolyureas.

The intermediate layer includes the nano-material having a particle sizeof 100 nm or less, present in an amount sufficient to adjust at leastone material property of the first polymer by 5% to 50% when compared tothe material property of the first polymer comprising a materialidentical to the nano-material but having a particle size greater than1000 nm.

The nano-material includes swellable layered materials; micaceousminerals; smectite minerals; carbon nanotubes; fullerenes; nanoscaletitanium oxides; iron oxides; ceramics; modified ceramics; metal andoxide powders; titanium dioxide particles; single-wall and multi-wallcarbon nanotubes; polymer nanofibers; carbon nanofibrils; nitrides;carbides; sulfides; ormocers; glass ionomers; resin-modified glassionomers; silicon ionomers; polymerizable cements; metal-oxide polymercomposites; lipid-based nanotubules, graphite sheets, or polyhedraloligomeric silsequioxanes.

Preferably, the swellable layered material sufficiently sorbs anintercalant polymer to increase the interlayer spacing between adjacentnano-materials to at least about 10 Å. Alternatively, the swellablelayered materials includes phyllosilicates, montmorillonite, sodiummontmorillonite; magnesium montmorillonite; calcium montmorillonite;nontronite; beidellite; volkonskoite; hectorite; saponite; sauconite;sobockite; stevensite; svinfordite; or vermiculite. The swellablelayered material may include phyllosilicates having a negative chargeranging from about 0.15 to about 0.9 charges per formula unit and acommensurate number of exchangeable metal cations. In a preferredembodiment, the nano-materials are chemically-modified. The cover layercan be formed solely of a polyurethane, a polyurea, a polyurea-urethane,or a polyurethane-urea.

A golf ball comprising a core comprising a first polymer comprising anacid group fully-neutralized by a salt of an organic acid, a cationsource, or a suitable base of the organic acid, the core having acompression of 100 or less and a diameter of between about 1.00 inchesand about 1.64 inches; and a cover layer; wherein the core comprises anano-material having an average particle size of 100 nm or less, presentin an amount sufficient to adjust at least one material property of thefirst polymer by 5% to 50% when compared to the material property of thefirst polymer comprising a material identical to the nano-material buthaving an average particle size greater than 1000 nm.

In one embodiment, the cover layer comprises a polymer selected from thegroup consisting of ionomeric copolymers and terpolymers, ionomerprecursors, thermoplastics, thermoplastic elastomers, polybutadienerubber, balata, grafted metallocene-catalyzed polymers, non-graftedmetallocene-catalyzed polymers, single-site polymers, high-crystallineacid polymers and their ionomers, cationic ionomers, anionic ionomers,polyurethanes, and polyureas.

The present invention is further directed to a golf ball including acore, an intermediate layer, and a cover. The core is formed from afirst polymer comprising an acid group fully-neutralized by a salt of anorganic acid, a cation source, or a suitable base of the organic acid,and a nano-material having an average particle size of 100 nm or lesspresent in a first amount. The intermediate layer, which is disposedbetween the core and the cover layer, is typically formed from a polymerselected from the group consisting of ionomeric copolymers andterpolymers, ionomer precursors, thermoplastics, thermoplasticelastomers, polybutadiene rubber, balata, grafted metallocene-catalyzedpolymers, non-grafted metallocene-catalyzed polymers, single-sitepolymers, high-crystalline acid polymers and their ionomers, cationicionomers, anionic ionomers, polyurethanes, and polyureas. The firstpolymer has a material property, and a second polymer, identical to thefirst polymer and comprising a second amount of a material identical tothe nano-material but having an average particle size greater than 1000nm, has substantially the same material property as the first polymer.The first amount is substantially less than the second amount.

DEFINITIONS

As used herein, the terms “nanoparticulate” and “nanoparticle” refer toaverage particle size diameters of 100 nm or less; it should beunderstood that nano-materials in cylindrical or tubular form may havelengths greater than 100 nm, typically as high as 1000 nm, but stillhave average diameters of 100 nm or less.

As used herein, the term “layered material” refers to an inorganicmaterial, such as a smectite clay mineral, that is in the form of aplurality of adjacent layers and has a typical thickness, for eachlayer, of about 100 Å.

As used herein, the terms “intercalate” or “intercalated” refer to alayered material that includes oligomer and/or polymer moleculesdisposed between adjacent layers of the layered material to increase theinterlayer spacing between the adjacent platelets to at least 10 Å.

As used herein, the terms “exfoliate” or “exfoliated” refer toindividual layers of an intercalated material so that adjacent layers ofthe intercalated material can be dispersed individually throughout acarrier material, such as a matrix polymer.

As used herein, the term “nanocomposite” refers to an oligomer, polymeror copolymer having dispersed therein an exfoliated and/or anintercalated material.

As used herein, the term “matrix polymer” refers to a thermoplastic orthermosetting polymer in which the exfoliate is dispersed to form ananocomposite.

DETAILED DESCRIPTION

The golf balls of the present invention include a core and a coversurrounding the core, at least one of which is formed from a compositioncomprising a nanoparticulate material or a blend of a nanoparticulatematerial with polymeric and/or rubber materials. The core and/or thecover may have more than one layer and an intermediate layer may bedisposed between the core and the cover of the golf ball. The golf ballcores of the present invention may comprise any of a variety ofconstructions. For example, the core of the golf ball may comprise asolid sphere or may be a solid center surrounded by at least oneintermediate or outer core layer. The center of the core may also be aliquid filled sphere surrounded by at least one core layer. Theintermediate layer or outer core layer may also comprise a plurality oflayers. The core may also comprise a solid or liquid filled centeraround which tensioned elastomeric material is wound. The cover layermay be a single layer or, for example, formed of a plurality of layers,such as an inner cover layer and an outer cover layer. A non-structurallayer, such as a water vapor barrier layer, may also be included betweenany two layers or even as a coating layer.

While the various golf ball centers, cores, and layers may be formed ofany materials known to those skilled in the art, the present inventionis particularly directed to compositions comprising nanoparticulates,the compositions being suitable for any of the above golf ballcomponents.

Nanoparticulates are generally divided into three categories: organic,inorganic, and metallic, all of which are suitable for use incompositions for golf ball components. Because of their sub-micron size(particle size of 100 nm or less), a higher concentration of particles(greater surface area) are available to interact with the surroundingpolymer or rubber materials, dramatically increasing their effect on theproperties of the compositions at concentrations much lower thanconventionally required. This, for example, might allow the golf ballconstruction to take on a form not previously available (i.e.,increasing weight of another layer as a result of the lower amount ofnanoparticulate (and therefore decreased weight) used.

Because the nanometer-sized particles have such a large surface area,small quantities of nanomaterials can have an intimate interactions andcompatibility with the host matrix, typically a polymeric material, notavailable to conventional-sized particles. These interactions can causesignificant property changes in the compositions. For example, a 3% to5% loading of nanoclay into a polymer blend will exhibit propertiessimilar to 20% to 60% loading of conventional reinforcing agents such askaolin, silica, talc, and carbon black. The resulting compositions aregenerally referred as “nanocomposites.” Preferably, the nanoparticles ofthe present invention have a surface area of at least about 100 m²/g,more preferably at least about 250 m²/g, and most preferably at leastabout 500 m²/g.

The nanomaterials typically have particle sizes ranging from about 0.9nm up to 100 nm in diameter and have an aspect ratio of about 100 toabout 1000. Any swellable layered material that sufficiently sorb theintercalant polymer to increase the interlayer spacing between adjacentplatelets to at least about 10 Å (when the phyllosilicate is measureddry) may be used. Useful swellable layered materials include, but arenot limited to, phyllosilicates, such as smectite clay minerals, e.g.,montmorillonite, particularly sodium montmorillonite; magnesiummontmorillonite; and/or calcium montmorillonite; nontronite; beidellite;volkonskoite; hectorite; saponite; sauconite; sobockite; stevensite;svinfordite; vermiculite; and the like.

Other useful layered materials include micaceous minerals, such asillite and mixed layered illite, and smectite minerals, such asledikite, and admixtures of illites with the clay minerals named above.Other layered materials having little or no charge on the layers may beuseful in this invention provided they can be intercalated with theintercalant polymers to expand their interlayer spacing to at leastabout 10 Å. Preferred swellable layered materials are phyllosilicates ofthe 2:1 type having a negative charge on the layers ranging from about0.15 to about 0.9 charges per formula unit and a commensurate number ofexchangeable metal cations in the interlayer spaces. Most preferredlayered materials are smectite clay minerals such as montmorillonite,nontronite, beidellite, volkonskoite, hectorite, saponite, sauconite,sobockite, stevensite, and svinfordite.

The interlayer spacing is measured when the layered material is “dry,”containing 3% to 6% by weight water, based on the dry weight of thelayered material. The preferred clay materials generally includeinterlayer cations, such as Na⁺, Ca⁺², K⁺, Mg⁺², NH₄ ⁺, and the like,including mixtures thereof.

Preferably, the compositions of the present invention comprise inorganicnanomaterials, such as chemically-modified montmorillonite clays andpolymer grade montmorillonites, commercially available from NanocorCompany of Arlington Heights, Ill., and CLOISITE®, commerciallyavailable from Southern Clay Products of Widner, United Kingdom.

The compositions of the present invention may also comprise organicnanomaterials like polyhedral oligomeric silsequioxanes, essentiallychemically modified nano-scale particles of silica. Examples of thesematerials include POSS®, commercially available from Hybrid Plastics ofFountain Valley, Calif.

The compositions of the present invention may also include othernanomaterials including, but not limited to, carbon nanotubes;fullerenes; nanoscale titanium oxides; iron oxides; ceramics; modifiedceramics, such as organic/inorganic hybrid polymers; metal and oxidepowders (ultrafine and superfine); titanium dioxide particles;single-wall and multi-wall carbon nanotubes; polymer nanofibers; carbonnanofibrils; nitrides; carbides; sulfides; gold nanoparticles; andmixtures thereof.

“Hybrid” nanomaterials are also suitable for the compositions of thepresent invention and include, but are not limited to, glass ionomers,ormocers, and other inorganic-organic materials. The “hybrid” materialsof the present invention may be described by a number of lexiconsincluding, but not limited to, glass ionomers, resin-modified glassionomers, silicon ionomers, dental cements or restorative compositions,polymerizable cements, metal-oxide polymer composites, and ionomercements.

Any of the “nanomaterials” disclosed herein may be chemically orphysically modified and/or further chemically or physically modified toenhance or alter properties.

Ormocers are composite materials formed of ceramic and polymer networksthat combine and interpenetrate with one another. The ormocers of thepresent invention typically have particle diameters in the range of fromabout 10 nm to about 300 nm. Preferably, the particle diameters are fromabout 20 nm to about 200 nm. The ormocers generally have a surface areaof about 4 m²/g to about 600 m²/g, more preferably about 10 m²/g toabout 50 m²/g.

Ormocers are also composite materials which have a network of organicand inorganic polymers intertwined in one another. The expression“network” designates a three-dimensional arrangement of substancescovalently bound to one another. The organic network fills empty sitesof the inorganic network, so that the two networks are firmly bound toone another. In this connection, inorganic means that the main chainsare formed, in particular, of —Si—O— bonds, which can be both linear aswell as branched. The Si atoms of the inorganic network can be replaced,partially, by other metal or semimetal atoms including, but not limitedto, Al, B, Zr, Y, Ba, and Ti. The organic network is obtained by thepolymerization of organic monomers, in particular, vinyl ether radicals,wherein other monomers, which can be copolymerized with vinyl etherradicals can be included. The organic network of ormocers, in accordancewith the invention, can be obtained by the hydrolytic condensation ofone or more silicon compounds, wherein preferred silicon compounds aremonomeric silanes.

Suitable ormocer production methods are disclosed in U.S. patentapplication Ser. No. 2001/0056197, filed Dec. 27, 2001, the disclosureof which is incorporated herein, in its entirely, by express referencethereto.

In accordance to an aspect of the invention, a moisture vapor barrierlayer, which can be formed from any material disclosed herein, may alsohave nanoparticulates, including ormocers, disposed therein. Vaporbarrier layers prevent or minimize the penetration of moisture,typically water vapor, into the core of the golf ball. The nanoparticlesare preferably hydrophobic and create a more tortuous path across themoisture vapor barrier layer to reduce the moisture transmission rate ofthe layer. The barrier layers may also include nanoscale ceramicparticles, flaked glass, and flaked metals (e.g., micaceous materials,iron oxide or aluminum). In one embodiment, ormocers are employed as awater vapor barrier layer disposed between the core and cover layers.Preferably, the moisture vapor barrier layer preferably has a moisturevapor transmission rate that is lower than that of the cover, and morepreferably less than the moisture vapor transmission rate of an ionomerresin such as SURLYN®, which is in the range of about 0.45 to about 0.95g·mm/m²·day. The moisture vapor transmission rate is generally measuredusing the ASTM F1249-90 and ASTM F372-99 standards.

Any of the disclosed nanoparticulates are effective as water vaporbarrier layers, and have the particular advantage of improving(decreasing) the water vapor transmission rate (“WVTR”) of layermaterials in their virgin state. Preferably, the WVTR is improved by10%, more preferably by 25%, most preferably by 50%. Optionally,ormocers (and/or other nanoparticulates) may be used in barrier layer(s)and/or coating layer(s), situated over the core, intermediate layers, orcover layers, most preferably over the cover layer.

Compositions comprising a liquid material and a powder material, whereinthe liquid material comprises 4-methacryloxyethyl trimellitic acid andwater and the powder material comprises a powdered fluoroaluminosilicate glass or a powdered metal oxide containing zinc oxide as themajor component, are also suitable. Other suitable materials includealuminofluorosilicate glasses having the following features: a ratio ofAl to Si of 0.57-1.12 by mass; a total content of Mg and Ba of 29-36% bymass; a ratio of Mg to Ba of 0.028-0.32 by mass; and a content of P of2-10% by mass. Fluoroaluminosilicate glass powders having a specificgravity of 2.4 to about 4.0, a mean particle size of 0.02 to 1 μm orless, and a BET specific surface area of 2.5 about 6.0 m²/g are alsosuitable. Preferably they have a maximum particle size of less than 100nm and contain 10 to about 21% by weight of Al³⁺, about 21% by weight ofSi⁴⁺, about 20% by weight of F⁻, and about 34% by weight in total ofSr²⁺ and/or Ca²⁺ in its components.

Glass powders for glass ionomer cements are also suitable hybridmaterials. These powders have a shape in which a major axis length isfrom 3 to 1,000 times a minor axis length, in a glass powder for glassionomer cement. The glass powder for glass ionomer cement having a shapein which a major axis length is from 3 to 1,000 times a minor axislength is a fibrous glass having a minor axis length of from 0.1 to 100nm and a major axis length of less than 100 nm, and its content iswithin a range of from 0.1 to 80% by weight.

Other suitable “hybrid” materials include a polymerizable compositioncomprising a polymerizable resin composition and a filler compositioncomprising a bound, nanostructured colloidal silica. These compositescomprise a resin composition and a filler composition, wherein thefiller composition comprises a nanostructured, bound silica, preferablyin the form of nanosized particles having their largest dimensions inthe range from about 10 to about 50 nm. Silica particles are preferablybound so as to result in chains having lengths in the range from about50 nm to about 400 nm.

One preferred composition comprises a binder and a filler wherein thefiller is comprised of about 1% to about 50% by weight alumina, about50% by weight to about 98% by weight silica, and boron. Anotherpreferred composition comprises: about 15% to about 30% by weightalumina fiber; about 65% to about 85% by weight silica fiber; about 1%to about 3% by weight silicon carbide; and about 1% to about 5% byweight boron nitride. Another more preferred fused-fibrous compositionfor the filler is as follows: about 21% by weight alumina fiber; about74% by weight silica fiber; about 2% by weight silicon carbide; andabout 2.85% by weight boron nitride. Preferably, the “hybrid” materialsof the present invention are comprised of alumina and silica fibers in aratio of 22:78.

Flexible composite hybrid compositions are provided comprising about 2to 15 weight percent of a flexible monomer portion comprising one ormore flexible co-monomers of the general formulaR¹—O—[(CH—R²)_(n)—O—]_(z)—R³ wherein R¹ and R3 are acrylate ormethacrylate functional groups, R² is selected from the group ofhydrogen, methyl and ethyl, n is from 3 to 5 and z is from about 3 toabout 20 and the monomers have average molecular weights from at leastabout 300 or higher; about 30 to about 80 weight percent of a fillerportion; about 18 to 60 weight percent of a comonomer portion comprisingone or more co-monomers capable of polymerizing with the flexiblemonomer portion; and a polymerization catalyst system for polymerizingand hardening the composition.

Suitable glass ionomer cements are generally comprised of a powdercomponent containing aluminosilicate and a liquid portion. Often theliquid portion is expressed as containing polyacrylic acid, polymaleicacid, polyitaconic acid, or a copolymer of at least two of the acids.The liquid portion may also comprise carboxylate polymers or carboxylicacid polymeric structures, such as those including acrylic acid, maleicacid, crotonic acid, isocrotonic acid, methacrylic acid, sorbic acid,cinnamic acid, fumaric acids, and the like. In most glass ionomercements, the primary reactions which cause the glass ionomer cement toharden is cross-linking, i.e., the cross-linking of polycarboxylatechains by metal ions from the glass. Also, during setting, the acids ofthe glass ionomer cement dissolve the glass structure to release metalconstituents of the glass. Metal carboxylates are formed during thesetting process. This may be distinguished from the primary settingreactions of acrylic cements which are other forms of polymerizationreactions. Though other forms of polymerization reactions may occur inglass ionomer cements, these reactions are secondary to thecross-linking reactions of the glass ionomer cement.

Polyalkenoate cements, such as glass-ionomers and zinc polycarboxylate,are also suitable. “Hybrid” compositions according to the presentinvention comprise a reaction product between an aluminosilicate glasspowder containing at least one element selected from Ca, Sr, and Ra andan organic acid containing one or more carboxyl groups in one moleculethereof; a methanol-insoluble polymer; a monomer containing at least oneunsaturated double bond and having no acidic group; a polymerizationinitiator; and, optionally, a filler.

“Hybrid” composite materials may be characterized by a substrate and bya nano-composite which is in functional contact with the substrate andis obtainable by surface modification of colloidal inorganic particleswith one or more silanes of the general formula (I) R_(x)—Si-A_(4-x)where the radicals A are identical or different and are hydroxyl groupsor groups which can be removed hydrolytically, except methoxy, theradicals R are identical or different and are groups which cannot beremoved hydrolytically and x is 0, 1, 2 or 3, where x≧1 in at least 50mol % of the silanes; under the conditions of the sol-gel process with abelow-stoichiometric amount of water, based on the hydrolysable groupswhich are present, with formation of a nano-composite sol, and furtherhydrolysis and condensation of the nano-composite sol, if desired,before it is brought into contact with the substrate, followed bycuring, said substrate not being a glass or mineral fiber or a vegetablematerial.

Ormocers, which can be obtained by the hydrolytic condensation of one ormore silicon compounds, and the subsequent polymerization of organicmonomers, wherein at least one silicon compound comprises vinyl etherradicals of formula:

wherein R represents hydrogen, methyl, or ethyl, are also suitable.Low-viscosity “hybrid” materials containing a non-settling nano-scalefiller are also suitable. The filler forms a stable sol withlow-viscosity materials and the filler may be prepared by surfacetreatment of fillers having a primary particle size of from about 1 toabout 100 nm.

Interwoven organic-inorganic solid composite materials are alsosuitable. These materials are formed of a mixture of a precursorpolymer, an alcohol, and a catalyst system. The precursor polymertypically has an inorganic polymer backbone of Si or Ti with linkages topolymerizable alkoxide groups. The catalyst system promotes thehydrolysis and polymerization of the alkoxide groups and thecondensation of the inorganic backbone to form a solid interwovennetwork with the organic polymer chains interpenetrating the network.

These “hybrid” materials and the nanoparticulates described herein arecontemplated for use in compositions for a variety of golf ballcomponents including, but are not limited to, golf ball centers, cores,layers, covers, coatings, and, additionally, continuous ornon-continuous layers such as those described in U.S. Pat. No.6,494,795, which is incorporated herein, in its entirety, by expressreference thereto.

Lipid-based nanotubules are also suitable nanomaterials for thecompositions of the present invention. Lipid tubules are aself-organizing system in which surfactants crystallize into tightlypacked bilayers that spontaneously form cylinders less than 100 nm indiameter. These novel cylindrical lipid structures, called nanotubules,can be used to entrap and release a variety of active compounds intosurrounding materials. One embodiment of the invention is directed tothe controlled release of desirable active agents or compounds,microencapsulated in nanotubules, by their dispersion in golf ballcoatings, paints, adhesives, and component compositions. The tubules canbe dispersed wet, aqueous or solvent-based, or dry, if robustness isrequired. Filled or unfilled nanotubules may also be used to adjustvirgin material properties.

Suitable tubules include those formed by the self organization ofpolymerizable lipid-based molecules. The tubules are typically formedfrom diacetylinic phosphatidylcholine by several different techniques,such as heating the lipid above the phase transition temperaturefollowed by slow cooling. Alternatively, the tubules can be formed byheating the lipid above the phase transition temperature, rapidlycooling the lipid to about 0° C., raising the temperature above thephase transition temperature a second time, and slowly cooling it toroom temperature. Other additional methods of forming the nanotubules ofthe present invention are envisioned. Naturally occurring nanotubules,such as halloycite, are also suitable for the present invention.

Alternatively, the nanotubules may additionally contain a metal (on theinner and/or outer surfaces). The tubules can be metallized with anymetal (or alloy thereof) capable of being plated. Metal tubules may beprepared by plating a metal on a filament which is soluble in ahydrocarbon solvent, to form an outer layer of metal, and then removingthe central filament by exposure to a hydrocarbon solvent.Alternatively, a porous membrane may be plated with a metal to form alayer of metal on the inside surface of the pores, dissolution of themembrane, and collection of the metal tubules. Once coated with metal,the tubules are filtered to remove the solvent and are air dried to apowder form. At this point the tubules can be stirred into a coating,such as a paint or adhesive, by gentle agitation. If the tubules areprocessed to a wet stage and then solvent exchanged with a coatingcompatible solvent, the tubules can be mixed directly into a coating orcomposition with a diluent solvent.

A critical aspect of the tubules is, of course, their dimensions.Suitable inner diameters for range from about 50 nm to about 1000 nm,preferably from about 100 nm to about 900 nm, and most preferably fromabout 200 nm to about 800 nm. The inner diameter of the tubules and thedesired time period of release may be controlled by varying theconditions used to produce the tubules. These include choice of activeagent, carrier, environment surrounding the tubule, and other componentsof the composition (if the tubules are present in a composition).Generally, the diameter of the tubule will be 2 to 1,000 times theaverage diameter of the active agent or compound, preferably 20 to 500times the average diameter. The nanotubules are not limited to those ofany specific length. For any given tubule the time of effectiveness willincrease with an increase in the length of the tubule.

Because of the tight packing of the surfactants in tubules, themicrostructures should dissolve from their ends only. Since the size ofthe end (the only available surface area for removal of active agent) isconstant until the tubule is annihilated, a population of tubules ofuniform length will release surfactant at a constant rate. A controlledrate of release of a compound from a coating or polymer matrix can beachieved by creating a porous structure of controlled dimensions withina coating. The compound must migrate through the coating to reach theinner or outer environment or adjacent materials. This structure can becreated by adding to a coating (or polymer composition) an effectiveamount of between about 5% and about 70% of nanotubules that contain orare composed of the desired active agent or compound.

The tubules, which act as nanovials or nanovessles, can be filled by avariety of techniques including capillary action. Compounds and activeagents include UV absorbers, light stabilizers, bleaching agents,fluorophores, healing agents, and catalysts. Suitable UV absorbers andlight stabilizers are described in U.S. application Ser. No.:10/627,504, the disclosure of which is incorporated herein, in itsentirety, by express reference thereto. Suitable healing agents aredescribed in U.S. Pat. No. 6,808,461, the disclosure of which isincorporated herein, in its entirety, by express reference thereto.

The rate of release of the compound as a function of area can be furthercontrolled by the “loading” of the nanotubules, the concentration of thecompound or agent contained in the tubules, the dimensions of thetubules, and solubility modifiers also contained within the nanotubules.The compound is chosen during the manufacture of the tubules, and itsrate of release can be further modified during encapsulation by theaddition of solubility modifiers such as glues, resins, polymers andother “slow release agents.”

The hardness and ablation rate of a coating is controlled by theselection of the resins used as the coating vehicle. Vinyl-resinmixtures, acrylics, polyurethanes, and epoxies have been usedsuccessfully for this purpose. Further control of the coating propertiesand the release rates of the toxicants can be controlled by theorientation and distribution of the tubules by two methods. Orientationcan be accomplished by coating the surface in the presence of a magneticor electrical field which creates a preferred orientation of the tubulesto the coated surface, either parallel or normal. In addition, incoatings where the film thickness is less than the average tubulelength, the tubules can be oriented parallel to the surface.

Because of the aspect ratio and size of the tubules, the tubules canfurther act to form, within the coating, a network which adds improvedphysical characteristics. At the least the tubules extend down into thesurface so that they are anchored in place. The ability to form acomposite structure within the coating may provide enhanced structuralproperties not normally associated with the coating or compositionwithin which the tubules are dispersed.

The present coatings and/or compositions (containing the nanotubules)may be applied to a surface by any conventional techniques. Thus, thecoating compositions may be applied by roller, brush, or spray over asuitable primer or barrier coating, if necessary. The tubules are easilydispersed in paint and may be applied by means commonly used in theapplication of paint coatings. In addition, the tubules may be dried,and metal or metallized tubules can be oxidized. Such oxidized tubulescan be charged and applied to oppositely charged surfaces byconventional powder coating technology. If the tubules are dispersed ina polymer blend or matrix, the composition may be further injection orcompression molded, as desired. Additionally, the nanotubules may bedispersed in any of the reactants in a casting or reaction injectionmolding process.

A carrier is used to “fill” the tubules with the desired compound oractive agent. The selection of the carrier is determined by theviscosity of the carrier and the solubility of the active agent in thecarrier. The carrier must possess a sufficiently low viscosity so thatit can fill the tubule as a result of capillary action.

If the agent is soluble or is mobile in the carrier, then the rate ofrelease depends on the diffusion rate and solubility of the agent in thecarrier and in the external matrix (if present). If the agent isinsoluble or immobile in the carrier, then the rate of release dependson the rate of release of the carrier itself from the tubule.

In the present context, release means delivery of the agent to asurrounding matrix (e.g., in a coating composition). Accordingly,suitable carriers include low molecular weight polymers and monomers.Specific examples of such polymers include polysaccharides; polyesters;polyamides; nylons; polypeptides; polyurethanes; polyureas,polyethylenes; polypropylenes; polyvinylchlorides; polystyrenes;polyphenols; polyvinyl pyrollidone; polyvinyl alcohol; ethylcellulose;gar gum; polyvinyl formal resin; water soluble epoxy resins;urea-formaldehyde; polylysine; chitosan; polyvinyl acetate andcopolymers; and mixtures thereof.

Other uses for the nanotubules may include adhesion; thin-layerenforcement or stability; custom indicia or novel cover layers (i.e.,metallized tubules blended with cover material, which, upon oxidation,form colored “swirls” or patterns); reactive identifiers (i.e., age,heat, moisture, impact frequency, etc.); inks; and dyes.

Methods and processes for forming selected microstructures havingpredetermined shape and dimension from surfactants are described in U.S.Pat. Nos. 4,877,501 and 4,990,291; methods necessary to coat tubular,spheroidal, and helical lipid microstructures with a range of metals aredescribed in U.S. Pat. No. 4,911,981; and tubules are useful in theproduction of coating compositions for the protection of surfaces cominginto contact with water, adhesive resins for the production of laminatedwood products, and devices for dispensing pesticides are described inU.S. Pat. No. 6,280,759, all of which are incorporated herein, in theirentirety, by express reference thereto.

In another embodiment, graphite nanosheets are used to form one or moreinner cover layers, but the golf ball of the present invention may beformed with a variety of constructions. Graphite typically consists of aplurality of layered planes of hexagonal arrays or networks of carbonatoms. The layered planes of hexagonally arranged carbon atoms aresubstantially flat and are oriented substantially parallel to oneanother. The carbon atoms on a single layered plane are covalentlybonded together, and the layered planes are bonded by substantiallyweaker van der Waals forces. Graphite is also an anisotropic structure,exhibits many properties that are highly directional, and possesses ahigh degree of orientation. Graphite includes natural graphite, Kishgraphite and synthetic graphite. Graphite fillers are availablecommercially in powder form from Asbury Graphite, Inc. in Asbury, N.J.and Poco Graphite Inc, in Decatur, Tex.

In accordance with a first preferred embodiment of the present inventionand as described in detail below, graphite is intercalated to insertatoms or molecules in the inter-planar spaces between the layeredplanes. The intercalated graphite is then expanded or exfoliated bysudden exposure to high heat to expand the inter-planar spacing betweenthe layered planes. The exfoliated graphite is then mixed with suitablemonomers and other additives prior to in situ polymerization to formnanosheets of graphite dispersed in a polymeric matrix. The polymericmatrix with graphite nanosheets dispersed therein may be formed into oneor more layers of a golf ball, or it may be blended with other polymersdescribed herein to form one or more layers of a golf ball.

A preferred method to intercalate graphite is immersing the graphite ina solution containing an oxidizing agent. Suitable oxidizing agentsinclude solutions containing nitric acid, potassium chlorate, chromicacid, potassium permanganate, potassium chromate, potassium dichromate,perchloric acid and the like, or mixtures, such as concentrated nitricacid and chlorate, chromic acid and phosphoric acid, sulfuric acid andnitric acid, or mixtures of a strong organic acid, e.g., trifluoroaceticacid, and a strong oxidizing agent soluble in the organic acid.

Preferably, the intercalating agent is a solution containing a mixtureof X/Y, wherein X can be sulfuric acid or sulfuric acid and phosphoricacid and Y is an oxidizing agent, such as nitric acid, perchloric acid,chromic acid, potassium permanganate, sodium nitrate, hydrogen peroxide,iodic or periodic acids. More preferably, the intercalating agent is asolution comprising about 80% by volume of sulfuric acid and 20% byvolume of nitric acid. Preferably, the graphite is immersed in thesulfuric and nitric acid solution for up to 24 hours, or more. Theresulting material, also known as graphite intercalated compound,comprises layered planes of carbon and intercalate layers stacked on topof one another in a periodic fashion. Typically, 1-5 layers of carboncan be present between adjacent intercalate layers. The preferredquantity of intercalated solution is from about 10 parts to about 150parts of solution to 100 parts of graphite, more preferably from about50 parts to about 120 parts to 100 parts of graphite.

Alternatively, the intercalating process can be achieved by otherchemical treatments. For example, the intercalating agents may include ahalogen, such as bromine, or a metal halide such as ferric chloride,aluminum chloride, or the like. A halogen, particularly bromine, may beintercalated by contacting graphite with bromine vapors, or with asolution of bromine in sulfuric acid, or with bromine dissolved in asuitable organic solvent. Metal halides can be intercalated bycontacting the graphite with a suitable metal halide solution. Forexample, ferric chloride can be intercalated by contacting graphite withan aqueous solution of ferric chloride, or with a mixture of ferricchloride and sulfuric acid.

Other suitable intercalating agents include, but are not limited to,chromyl chloride, sulfur trioxide, antimony trichloride,chromium(III)chloride, iodine chloride, chromium(IV)oxide,gold(III)chloride, indium chloride, platinum(IV)chloride, chromylfluoride, tantalum(V)chloride, samarium chloride, zirconium(IV)chloride,uranium chloride, and yttrium chloride.

The intercalated graphite is then washed with water until excessintercalating agent is washed from the graphite, or if acid is useduntil the washed water pH value is neutral. The graphite is thenpreferably heated to above the boiling point of the washed solution toevaporate the washed solution. Alternatively, to eliminate thepost-intercalation washing step the amount of intercalated solution maybe reduced to about 10 parts to about 50 parts per 100 parts of graphiteas disclosed in U.S. Pat. No. 4,895,713, incorporated herein byreference.

To expand or exfoliate the inter-planar spacing between the layeredplanes, the intercalated graphite is exposed to very high heat in arelatively short amount of time. Without being bound by any particulartheory, the exfoliated mechanism is the decomposition of the trappedintercalating agent, such as sulfuric and nitric acids (H₂SO₄+HNO₃),between the highly oriented layered planes when exposed to heat.

Suitable exfoliated processes include heating the intercalated graphitefor a few seconds at temperatures of at least greater than 500° C., morepreferably greater than 700° C., and more typically 1000° C. or more.The treated graphite typically expands in the “c” direction about 100 tomore than 300 times the pre-treatment thickness. In one preferredexfoliating process, the intercalated graphite is exposed to temperatureof about 1050° C. for about 15 seconds to achieve a thickness in the “c”direction of about 300 times of that in the pre-exfoliated graphite.

The exfoliated graphite is then mixed with a monomer and heated to thepolymerization or vulcanization temperature to form a polymer withnanosheets of exfoliated graphite dispersed therein. The exfoliatedgraphite also reacts with the monomer to become a part of the structureof the polymer. It has also been shown that the nanosheets retained itsstructure in the polymer matrix, and that the monomer or polymer enteredthe gallery spacing between the nanosheets. It has also been determinedthat the dispersion of nanosheets of exfoliated graphite in thepolymeric matrix improves the tensile strength of the polymer. Thisimproved tensile strength of the polymer/graphite composite improves itsimpact strength.

The polymeric matrix can be any polymeric composition that is compatiblewith carbon. Suitable polymeric compositions include thermosettingpolymers and thermoplastic polymers. More particularly, suitablepolymeric compositions include polyethylene, polypropylene, acrylic andmethacrylic polymers such as polymethyl methacrylate, polystyrene,polyepoxides or any polymer comprising an epoxy moiety,phenol-formaldehydes, polyamides, polyesters, polyvinyl chlorides,polycarbonates, polyacetals, polytetrafluoroethylene, polyvinylidenefluoride, polyurethanes, copolymers and blends of same and the like.

Suitable polymeric compositions also include, but not limited to, one ormore of partially- or fully-neutralized ionomers including thoseneutralized by a metal ion source wherein the metal ion is the salt ofan organic acid, polyolefins including polyethylene, polypropylene,polybutylene and copolymers thereof including polyethylene acrylic acidor methacrylic acid copolymers, or a terpolymer of ethylene, a softeningacrylate class ester such as methyl acrylate, n-butyl-acrylate oriso-butyl-acrylate, and a carboxylic acid such as acrylic acid ormethacrylic acid (e.g., terpolymers including polyethylene-methacrylicacid-n or iso-butyl acrylate and polyethylene-acrylic acid-methylacrylate, polyethylene ethyl or methyl acrylate, polyethylene vinylacetate, polyethylene glycidyl alkyl acrylates). Suitable polymers alsoinclude metallocene catalyzed polyolefins, polyesters, polyamides,non-ionomeric thermoplastic elastomers, copolyether-esters,copolyether-amides, thermoplastic or thermosetting polyurethanes,polyureas, polyurethane ionomers, epoxies, polycarbonates,polybutadiene, polyisoprene, and blends thereof. Suitable polymericmaterials also include those listed in U.S. Pat. Nos. 5,919,100,6,187,864, 6,232,400, 6,245,862, 6,290,611, 6,353,058, 6,204,331 and6,142,887 and in PCT Publication Nos. WO 00/23519 and WO 01/29129, allincorporated herein. Ionomers, ionomer blends, thermosetting orthermoplastic polyurethanes, metallocenes are also suitable materials.

Most preferably, the polymer matrix materials include natural rubber,stryene-butadiene rubber, stryene-propylene or ethylene-diene blockcopolymer rubber, polyisoprene, polybutadiene, copolymers comprisingethylene or propylene such as ethylene-propylene rubber (EPR) orethylene-propylene diene monomer (EPDM) elastomer, copolymers ofacrylonitrile and a diene comprising elastomer (such as butadiene),polychloroprene and any copolymer including chloroprene, butyl rubber,halogenated butyl rubber, polysulfide rubber, silicone comprisingpolymers.

Exfoliated graphite may also be bonded with organic char materials, suchas coal tar pitches, asphalts, phenol-formaldehyde, urea-formaldehyde,polyvinylidene chloride, polyacrylonitrile, sugars, and saccharides,inorganic glass bonding agents, such as boric oxide, silica,phosphorous, pentoxide, germanium oxide, vanadium pentoxide, andinorganic salts, such as beryllium fluoride, sulfates, chlorides andcarbonates.

Alternatively, hydrogen peroxide can be blended with the intercalatingagent, preferably sulfuric acid, and agitated untilgraphite-hydrogensulfate compound is formed. The compound is thenremoved from the intercalating solution and washed. Thegraphite-hydrogensulfate compound is exfoliated as described above toform the exfoliated compound. This compound has properties that aresimilar to the exfoliated graphite. Advantageously, the process ofproducing graphite-hydrogensulfate compound releases less pollutantsinto the environment. This method is described in U.S. Pat. No.4,091,083, incorporated herein by reference.

Additionally, the nanosheets/polymeric matrix composite may be groundedor crushed and then mixed or blended with a second encasing polymericmaterial to produce a layer on the golf ball. Suitable polymericmaterials for the polymeric matrix discussed above are also suitable tobe second encasing material. Preferably, the polymeric matrix materialis methyl methacrylate and the second encasing polymeric material is apolyurethane or a natural or synthetic rubber, preferably polybutadiene.

The nanomaterials can be blended with thermoplastics, thermoplasticelastomers, rubbers, and thermoset materials useful in making golf ballcomponents. The nanoparticulates can be incorporated either duringblending operation such as in single or twin-screw extruders or inrubber mixing equipment like brabender or internal mixers. Also, thenanoparticulates can be blended in a reactor during the polymerizationof thermoplastic or thermoset or rubbery materials.

The materials for solid cores, which can be blended with the abovenanoparticulates, typically include compositions having a base rubber, acrosslinking agent, a filler, and a co-crosslinking or initiator agent.The base rubber typically includes natural or synthetic rubbers. Apreferred base rubber is 1,4-polybutadiene having a cis-structure of atleast 40%. Most preferably, the base rubber compriseshigh-Mooney-viscosity rubber but it should be understood that rubbershaving Mooney viscosity of any value are acceptable. Preferably, thebase rubber has a Mooney viscosity of between about 30 and about 120. Ifdesired, the polybutadiene can also be mixed with other elastomers knownin the art such as natural rubber, polyisoprene rubber and/orstyrene-butadiene rubber in order to modify the properties of the core.

The crosslinking agent includes a metal salt of an unsaturated fatty ornon-fatty acid such as a zinc salt or a magnesium salt of an unsaturatedfatty or non-fatty acid having 3 to 8 carbon atoms such as acrylic ormethacrylic acid. Suitable cross linking agents include one or moremetal salt diacrylates, dimethacrylates and monomethacrylates whereinthe metal is magnesium, calcium, zinc, aluminum, sodium, lithium ornickel. Preferred acrylates include zinc acrylate, zinc diacrylate, zincmethacrylate, and zinc dimethacrylate, and mixtures thereof. Thecrosslinking agent is typically present in an amount greater than about10 phr of the polymer component, preferably from about 10 to 40 phr ofthe polymer component, more preferably from about 10 to 30 phr of thepolymer component.

The initiator agent can be any known polymerization initiator whichdecomposes during the cure cycle. Suitable initiators include peroxidecompounds such as dicumyl peroxide, 1,1-di(t-butylperoxy)3,3,5-trimethyl cyclohexane, a-a bis(t-butylperoxy) diisopropylbenzene,2,5-dimethyl-2,5 di(t-butylperoxy) hexane or di-t-butyl peroxide andmixtures thereof.

Density-adjusting fillers typically include materials such as tungsten,zinc oxide, barium sulfate, silica, calcium carbonate, zinc carbonate,metals, metal oxides and salts, regrind (recycled core materialtypically ground to about 30 mesh particle), high-Mooney-viscosityrubber regrind, and the like.

Fillers added to one or more portions of the golf ball typically includeprocessing aids or compounds to affect Theological and mixingproperties, density-modifying fillers, tear strength, or reinforcementfillers, and the like. The fillers are generally inorganic, and suitablefillers include numerous metals or metal oxides, such as zinc oxide andtin oxide, as well as barium sulfate, zinc sulfate, calcium carbonate,barium carbonate, clay, tungsten, tungsten carbide, an array of silicas,and mixtures thereof. Fillers may also include various foaming agents orblowing agents which may be readily selected by one of ordinary skill inthe art. Fillers may include polymeric, ceramic, metal, and glassmicrospheres may be solid or hollow, and filled or unfilled. Fillers aretypically also added to one or more portions of the golf ball to modifythe density thereof to conform to uniform golf ball standards. Fillersmay also be used to modify the weight of the center or at least oneadditional layer for specialty balls, e.g., a lower weight ball ispreferred for a player having a low swing speed.

The invention also includes a method to convert the cis-isomer of thepolybutadiene resilient polymer component to the trans-isomer during amolding cycle and to form a golf ball. A variety of methods andmaterials have been disclosed in U.S. Pat. No. 6,162,135 and U.S.application Ser. No. 09/461,736, filed Dec. 16, 1999; Ser. No.09/458,676, filed Dec. 10, 1999; and Ser. No. 09/461,421, filed Dec. 16,1999, each of which are incorporated herein, in their entirety, byreference.

The golf ball components, preferably centers and/or core layers, of thepresent invention may also be formed from, or include as a blend,highly-neutralized polymers (“HNP”). The acid moieties of the HNP's,typically ethylene-based ionomers, are preferably neutralized greaterthan about 70%, more preferably greater than about 90%, and mostpreferably at least about 100%. The HNP's can be also be blended with asecond polymer component, which, if containing an acid group, may beneutralized in a conventional manner, by organic fatty acids, or both.The second polymer component, which may be partially- orfully-neutralized, preferably comprises ionomeric copolymers andterpolymers, ionomer precursors, thermoplastics, polyamides,polycarbonates, polyesters, polyurethanes, polyureas, thermoplasticelastomers, polybutadiene rubber, balata, metallocene-catalyzed polymers(grafted and non-grafted), single-site polymers, high-crystalline acidpolymers, cationic ionomers, and the like. HNP polymers typically have amaterial hardness of between about 20 and about 80 Shore D, and aflexural modulus of between about 3,000 psi and about 200,000 psi.

In one embodiment of the present invention the HNP's are ionomers and/ortheir acid precursors that are preferably neutralized, either filly orpartially, with organic acid copolymers or the salts thereof. The acidcopolymers are preferably α-olefin, such as ethylene, C₃₋₈α,β-ethylenically unsaturated carboxylic acid, such as acrylic andmethacrylic acid, copolymers. They may optionally contain a softeningmonomer, such as alkyl acrylate and alkyl methacrylate, wherein thealkyl groups have from 1 to 8 carbon atoms.

The acid copolymers can be described as E/X/Y copolymers where E isethylene, X is an α,β-ethylenically unsaturated carboxylic acid, and Yis a softening comonomer. In a preferred embodiment, X is acrylic ormethacrylic acid and Y is a C₁₋₈ alkyl acrylate or methacrylate ester. Xis preferably present in an amount from about 1 to about 35 weightpercent of the polymer, more preferably from about 5 to about 30 weightpercent of the polymer, and most preferably from about 10 to about 20weight percent of the polymer. Y is preferably present in an amount fromabout 0 to about 50 weight percent of the polymer, more preferably fromabout 5 to about 25 weight percent of the polymer, and most preferablyfrom about 10 to about 20 weight percent of the polymer.

Specific acid-containing ethylene copolymers include, but are notlimited to, ethylene/acrylic acid/n-butyl acrylate, ethylene/methacrylicacid/n-butyl acrylate, ethylene/methacrylic acid/iso-butyl acrylate,ethylene/acrylic acid/iso-butyl acrylate, ethylene/methacrylicacid/n-butyl methacrylate, ethylene/acrylic acid/methyl methacrylate,ethylene/acrylic acid/methyl acrylate, ethylene/methacrylic acid/methylacrylate, ethylene/methacrylic acid/methyl methacrylate, andethylene/acrylic acid/n-butyl methacrylate. Preferred acid-containingethylene copolymers include, ethylene/methacrylic acid/n-butyl acrylate,ethylene/acrylic acid/n-butyl acrylate, ethylene/methacrylic acid/methylacrylate, ethylene/acrylic acid/ethyl acrylate, ethylene/methacrylicacid/ethyl acrylate, and ethylene/acrylic acid/methyl acrylatecopolymers. The most preferred acid-containing ethylene copolymers are,ethylene/(meth) acrylic acid/n-butyl, acrylate, ethylene/(meth)acrylicacid/ethyl acrylate, and ethylene/(meth) acrylic acid/methyl acrylatecopolymers.

Ionomers are typically neutralized with a metal cation, such as Li, Na,Mg, or Zn. It has been found that by adding sufficient organic acid orsalt of organic acid, along with a suitable base, to the acid copolymeror ionomer, however, the ionomer can be neutralized, without losingprocessability, to a level much greater than for a metal cation.Preferably, the acid moieties are neutralized greater than about 80%,preferably from 90-100%, most preferably 100%, without losingprocessability. This accomplished by melt-blending an ethyleneα,β-ethylenically unsaturated carboxylic acid copolymer, for example,with an organic acid or a salt of organic acid, and adding a sufficientamount of a cation source to increase the level of neutralization of allthe acid moieties (including those in the acid copolymer and in theorganic acid) to greater than 90%, (preferably 100%).

The organic acids of the present invention are aliphatic, mono- ormulti-functional (saturated, unsaturated, or multi-unsaturated) organicacids. Salts of these organic acids may also be employed. The salts oforganic acids of the present invention include the salts of barium,lithium, sodium, zinc, bismuth, chromium, cobalt, copper, potassium,strontium, titanium, tungsten, magnesium, cesium, iron, nickel, silver,aluminum, tin, or calcium, salts of fatty acids, particularly stearic,bebenic, erucic, oleic, linoelic or dimerized derivatives thereof. It ispreferred that the organic acids and salts of the present invention berelatively non-migratory (they do not bloom to the surface of thepolymer under ambient temperatures) and non-volatile (they do notvolatilize at temperatures required for melt-blending).

The ionomers of the invention may also be partially neutralized withmetal cations. The acid moiety in the acid copolymer is neutralizedabout 1 to about 100%, preferably at least about 40 to about 100%, andmore preferably at least about 90 to about 100%, to form an ionomer by acation such as lithium, sodium, potassium, magnesium, calcium, barium,lead, tin, zinc, aluminum, or a mixture thereof.

The acid copolymers are generally prepared from ‘direct’ acidcopolymers, copolymers polymerized by adding all monomerssimultaneously, or by grafting of at least one acid-containing monomeronto an existing polymer.

Thermoplastic polymer components, such as copolyetheresters,copolyesteresters, copolyetheramides, elastomeric polyolefins, styrenediene block copolymers and their hydrogenated derivatives,copolyesteramides, thermoplastic polyurethanes, such ascopolyetherurethanes, copolyesterurethanes, copolyureaurethanes,epoxy-based polyurethanes, polycaprolactone-based polyurethanes,polyureas, and polycarbonate-based polyurethanes fillers, and otheringredients, if included, can be blended in either before, during, orafter the acid moieties are neutralized, thermoplastic polyurethanes.

The copolyetheresters are comprised of a multiplicity of recurring longchain units and short chain units joined head-to-tail through esterlinkages, the long chain units being represented by the formula:

and the short chain units being represented by the formula:

where G is a divalent radical remaining after the removal of terminalhydroxyl groups from a poly(alkylene oxide) glycol having a molecularweight of about 400-8000 and a carbon to oxygen ratio of about 2.0-4.3;R is a divalent radical remaining after removal of hydroxyl groups froma diol having a molecular weight less than about 250; provided saidshort chain ester units amount to about 15-95 percent by weight of saidcopolyetherester. The preferred copolyetherester polymers are thosewhere the polyether segment is obtained by polymerization oftetrahydrofuran and the polyester segment is obtained by polymerizationof tetramethylene glycol and phthalic acid. For purposes of theinvention, the molar ether-ester ratio can vary from 90:10 to 10:80;preferably 80:20 to 60:40; and the Shore D hardness is less than 70;preferably less than about 40.

The copolyetheramides are comprised of a linear and regular chain ofrigid polyamide segments and flexible polyether segments, as representedby the general formula:

wherein PA is a linear saturated aliphatic polyamide sequence formedfrom a lactam or amino acid having a hydrocarbon chain containing 4 to14 carbon atoms or from an aliphatic C₆-C8 diamine, in the presence of achain-limiting aliphatic carboxylic diacid having 4-20 carbon atoms;said polyamide having an average molecular weight between 300 and15,000; and PB is a polyoxyalkylene sequence formed from linear orbranched aliphatic polyoxyalkylene glycols, mixtures thereof orcopolyethers derived therefrom, said polyoxyalkylene glycols having amolecular weight of less than or equal to 6000; and n indicates asufficient number of repeating units so that said polyetheramidecopolymer has an intrinsic viscosity of from about 0.6 to about 2.05.The preparation of these polyetheramides comprises the step of reactinga dicarboxylic polyamide, the COOH groups of which are located at thechain ends, with a polyoxyalkylene glycol hydroxylated at the chainends, in the presence of a catalyst such as a tetra-alkyl ortho titanatehaving the general formula Ti(OR)_(x) wherein R is a linear branchedaliphatic hydrocarbon radical having 1 to 24 carbon atoms. Again, themore polyether units incorporated into the copolyetheramide, the softerthe polymer. The ether:amide ratios are as described above for theether:ester ratios, as is the Shore D hardness.

The elastomeric polyolefins are polymers composed of ethylene and higherprimary olefins such as propylene, hexene, octene, and optionally1,4-hexadiene and or ethylidene norbornene or norbomadiene. Theelastomeric polyolefins can be optionally functionalized with maleicanhydride, epoxy, hydroxy, amine, carboxylic acid, sulfonic acid, orthiol groups.

Thermoplastic polyurethanes are linear or slightly chain branchedpolymers consisting of hard blocks and soft elastomeric blocks. They areproduced by reacting soft hydroxy terminated elastomeric polyethers orpolyesters with diisocyanates, such as methylene diisocyanate (“MDI”),p-phenylene diisocyanate (“PPDI”), or toluene diisocyanate (“TDI”).These polymers can be chain extended with glycols, secondary diamines,diacids, or amino alcohols. The reaction products of the isocyanates andthe alcohols are called urethanes and these blocks are relatively hardand high melting. These hard high melting blocks are responsible for thethermoplastic nature of the polyurethanes.

Block styrene diene copolymers and their hydrogenated derivatives arecomposed of polystyrene units and polydiene units. They may also befunctionalized with moieties such as OH, NH₂, epoxy, COOH, and anhydridegroups. The polydiene units are derived from polybutadiene, polyisopreneunits or copolymers of these two. In the case of the copolymer it ispossible to hydrogenate the polyolefin to give a saturated rubberybackbone segments. These materials are usually referred to as SBS, SIS,or SEBS thermoplastic elastomers and they can also be functionalizedwith maleic anhydride.

Grafted metallocene-catalyzed polymers are also useful for blending withthe HNP's. The grafted metallocene-catalyzed polymers, whileconventionally neutralized with metal cations, may also be neutralized,either partially for fully, with organic acids or salts thereof and anappropriate base. Grafted metallocene-catalyzed polymers useful, such asthose disclosed in U.S. Pat. Nos. 5,703,166; 5,824,746; 5,981,658; and6,025,442, which are incorporated herein by reference, in the golf ballsof the invention are available in experimental quantities from DuPontunder the tradenames SURLYN® NMO 525D, SURLYN® NMO 524D, and SURLYN® NMO499D, all formerly known as the FUSABOND® family of polymers, or may beobtained by subjecting a non-grafted metallocene-catalyzed polymer to apost-polymerization reaction to provide a grafted metallocene-catalyzedpolymer with the desired pendant group or groups. Examples ofmetallocene-catalyzed polymers to which functional groups may be graftedfor use in the invention include, but are not limited to, homopolymersof ethylene and copolymers of ethylene and a second olefin, preferably,propylene, butene, pentene, hexene, heptene, octene, and norbomene.Generally, the invention includes golf balls having at least one layercomprising at least one grafted metallocene-catalyzed polymer or polymerblend, where the grafted metallocene-catalyzed polymer is produced bygrafting a functional group onto a metallocene-catalyzed polymer havingthe formula:

wherein R₁ is hydrogen, branched or straight chain alkyl such as methyl,ethyl, propyl, butyl, pentyl, hexyl, heptyl, and octyl, carbocyclic, oraromatic; R₂ is hydrogen, lower alkyl including C₁-C₅; carbocyclic, oraromatic; R₃ is hydrogen, lower alkyl including C₁-C₅, carbocyclic, oraromatic; R₄ is selected from the group consisting of H, C_(n)H_(2n+1),where n=1 to 18, and phenyl, in which from 0 to 5 H within R₄ can bereplaced by substituents COOH, SO₃H, NH₂, F, Cl, Br, I, OH, SH,silicone, lower alkyl esters and lower alkyl ethers, with the provisothat R₃ and R₄ can be combined to form a bicyclic ring; R₅ is hydrogen,lower alkyl including C₁-C₅, carbocyclic, or aromatic; R₆ is hydrogen,lower alkyl including C₁-C₅, carbocyclic, or aromatic; and wherein x, yand z are the relative percentages of each co-monomer. X can range fromabout 1 to 99 percent or more preferably from about 10 to about 70percent and most preferred, from about 10 to 50 percent. Y can be from99 to 1 percent, preferably, from 90 to 30 percent, or most preferably,90 to 50 percent. Z can range from about 0 to about 49 percent. One ofordinary skill in the art would understand that if an acid moiety ispresent as a ligand in the above polymer that it may be neutralized upto 100% with an organic fatty acid as described above.

Metallocene-catalyzed copolymers or terpolymers can be random or blockand may be isotactic, syndiotactic, or atactic. The pendant groupscreating the isotactic, syndiotactic, or atactic polymers are chosen todetermine the interactions between the different polymer chains makingup the resin to control the final properties of the resins used in golfball covers, centers, or intermediate layers. As will be clear to thoseskilled in the art, grafted metallocene-catalyzed polymers useful in theinvention that are formed from metallocene-catalyzed random or blockcopolymers or terpolymers will also be random or block copolymers orterpolymers, and will have the same tacticity of themetallocene-catalyzed polymer backbone.

As used herein, the term “phrase branched or straight chain alkyl” meansany substituted or unsubstituted acyclic carbon-containing compounds.Examples of alkyl groups include lower alkyl, for example, methyl,ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl or t-butyl; upper alkyl,for example, octyl, nonyl, decyl, and the like; and lower alkylene, forexample, ethylene, propylene, butylene, pentene, hexene, octene,norbornene, nonene, decene, and the like.

In addition, such alkyl groups may also contain various substituents inwhich one or more hydrogen atoms has been replaced by a functionalgroup. Functional groups include, but are not limited to hydroxyl,amino, carboxyl, sulfonic amide, ester, ether, phosphates, thiol, nitro,silane and halogen (fluorine, chlorine, bromine and iodine), to mentionbut a few.

As used herein, the term “substituted and unsubstituted carbocyclic”means cyclic carbon-containing compounds, including, but not limited tocyclopentyl, cyclohexyl, cycloheptyl, and the like. Such cyclic groupsmay also contain various substituents in which one or more hydrogenatoms has been replaced by a functional group. Such functional groupsinclude those described above, and lower alkyl groups having from 1-28carbon atoms. The cyclic groups of the invention may further comprise aheteroatom.

As mentioned above, R₁ and R₂ can also represent any combination ofalkyl, carbocyclic or aryl groups, for example, 1-cyclohexylpropyl,benzyl cyclohexylmethyl, 2-cyclohexylpropyl, 2,2-methylcyclohexylpropyl,2,2-methylphenylpropyl, and 2,2-methylphenylbutyl.

Non-grafted metallocene-catalyzed polymers useful in the presentinvention are commercially available under the trade name AFFINITY®polyolefin plastomers and ENGAGE® polyolefin elastomers commerciallyavailable from Dow Chemical Company and DuPont-Dow. Other commerciallyavailable metallocene-catalyzed polymers can be used, such as EXACT®,commercially available from Exxon and INSIGHT®, commercially availablefrom Dow. The EXACT® and INSIGHT® line of polymers also have novelrheological behavior in addition to their other properties as a resultof using a metallocene catalyst technology. Metallocene-catalyzedpolymers are also readily available from Sentinel Products Corporationof Hyannis, Mass., as foamed sheets for compression molding.

Monomers useful in the present invention include, but are not limitedto, olefinic monomers having, as a functional group, sulfonic acid,sulfonic acid derivatives, such as chlorosulfonic acid, vinyl ethers,vinyl esters, primary, secondary, and tertiary amines, mono-carboxylicacids, dicarboxylic acids, partially or fully ester-derivatizedmono-carboxylic and dicarboxylic acids, anhydrides of dicarboxylicacids, and cyclic imides of dicarboxylic acids.

In addition, metallocene-catalyzed polymers may also be functionalizedby sulfonation, carboxylation, or the addition of an amine or hydroxygroup. Metallocene-catalyzed polymers functionalized by sulfonation,carboxylation, or the addition of a hydroxy group may be converted toanionic ionomers by treatment with a base. Similarly,metallocene-catalyzed polymers functionalized by the addition of anamine may be converted to cationic ionomers by treatment with an alkylhalide, acid, or acid derivative.

The most preferred monomer is maleic anhydride, which, once attached tothe metallocene-catalyzed polymer by the post-polymerization reaction,may be further subjected to a reaction to form a graftedmetallocene-catalyzed polymer containing other pendant or functionalgroups. For example, reaction with water will convert the anhydride to adicarboxylic acid; reaction with ammonia, alkyl, or aromatic amine formsan amide; reaction with an alcohol results in the formation of an ester;and reaction with base results in the formation of an anionic ionomer.

The HNP's may also be blended with single-site and metallocene catalystsand polymers formed therefrom. As used herein, the term “single-sitecatalyst,” such as those disclosed in U.S. Pat. No. 6,150,462 which isincorporated herein by reference, refers to a catalyst that contains anancillary ligand that influences the stearic and electroniccharacteristics of the polymerizing site in a manner that preventsformation of secondary polymerizing species. The term “metallocenecatalyst” refers to a single-site catalyst wherein the ancillary ligandsare comprising substituted or unsubstituted cyclopentadienyl groups, andthe term “non-metallocene catalyst” refers to a single-site catalystother than a metallocene catalyst.

Non-metallocene single-site catalysts include, but are not limited to,the Brookhart catalyst, which has the following structure:

wherein M is nickel or palladium; R and R′ are independently hydrogen,hydrocarbyl, or substituted hydrocarbyl; Ar is (CF₃)₂C₆H₃, and X isalkyl, methyl, hydride, or halide; the McConville catalyst, which hasthe structure:

wherein M is titanium or zirconium. Iron (II) and cobalt (II) complexeswith 2,6-bis(imino) pyridyl ligands, which have the structure:

where M is the metal, and R is hydrogen, alkyl, or hydrocarbyl. Titaniumor zirconium complexes with pyrroles as ligands also serve assingle-site catalysts. These complexes have the structure:

where M is the metal atom; m and n are independently 1 to 4, andindicate the number of substituent groups attached to the aromaticrings; R_(m) and R_(n) are independently hydrogen or alkyl; and X ishalide or alkyl. Other examples include diimide complexes of nickel andpalladium, which have the structure:

where Ar is aromatic, M is the metal, and X is halide or alky.Boratabenzene complexes of the Group IV or V metals also function assingle-site catalysts. These complexes have the structure:

where B is boron and M is the metal atom.

As used herein, the term “single-site catalyzed polymer” refers to anypolymer, copolymer, or terpolymer, and, in particular, any polyolefinpolymerized using a single-site catalyst. The term “non-metallocenesingle-site catalyzed polymer” refers to any polymer, copolymer, orterpolymer, and, in particular, any polyolefin polymerized using asingle-site catalyst other than a metallocene-catalyst. The catalystsdiscussed above are examples of non-metallocene single-site catalysts.The term “metallocene catalyzed polymer” refers to any polymer,copolymer, or terpolymer, and, in particular, any polyolefin,polymerized using a metallocene catalyst.

As used herein, the term “single-site catalyzed polymer blend” refers toany blend of a single-site catalyzed polymer and any other type ofpolymer, preferably an ionomer, as well as any blend of a single-sitecatalyzed polymer with another single-site catalyzed polymer, including,but not limited to, a metallocene-catalyzed polymer.

The terms “grafted single-site catalyzed polymer” and “graftedsingle-site catalyzed polymer blend” refer to any single-site catalyzedpolymer or single-site catalyzed polymer blend in which the single-sitecatalyzed polymer has been subjected to a post-polymerization reactionto graft at least one functional group onto the single-site catalyzedpolymer. A “post-polymerization reaction” is any reaction that occursafter the formation of the polymer by a polymerization reaction.

The single-site catalyzed polymer, which may be grafted, may also beblended with polymers, such as non-grafted single-site catalyzedpolymers, grafted single-site catalyzed polymers, ionomers, andthermoplastic elastomers. Preferably, the single-site catalyzed polymeris blended with at least one ionomer of the preset invention.

Grafted single-site catalyzed polymers useful in the golf balls of theinvention may be obtained by subjecting a non-grafted single-sitecatalyzed polymer to a post-polymerization reaction to provide a graftedsingle-site catalyzed polymer with the desired pendant group or groups.Examples of single-site catalyzed polymers to which functional groupsmay be grafted for use in the invention include, but are not limited to,homopolymers of ethylene and propylene and copolymers of ethylene and asecond olefin, preferably, propylene, butene, pentene, hexene, heptene,octene, and norbomene. Monomers useful in the present invention include,but are not limited to olefinic monomers having as a functional groupsulfonic acid, sulfonic acid derivatives, such as chlorosulfonic acid,vinyl ethers, vinyl esters, primary, secondary, and tertiary amines,epoxies, isocyanates, mono-carboxylic acids, dicarboxylic acids,partially or fully ester derivatized mono-carboxylic and dicarboxylicacids, anhydrides of dicarboxylic acids, and cyclic imides ofdicarboxylic acids. Generally, this embodiment of the invention includesgolf balls having at least one layer comprising at least one graftedsingle-site catalyzed polymer or polymer blend, where the graftedsingle-site catalyzed polymer is produced by grafting a functional grouponto a single-site catalyzed polymer having the formula:

where R₁ is hydrogen, branched or straight chain alkyl such as methyl,ethyl, propyl, butyl, pentyl, hexyl, heptyl, and octyl, carbocyclic,aromatic or heterocyclic; R₂, R₃, R₅, and R₆ are hydrogen, lower alkylincluding C₁-C₅, carbocyclic, aromatic or heterocyclic; R₄ is H,C_(n)H_(2n+1), where n=1 to 18, and phenyl, in which from 0 to 5 Hwithin R₄ can be replaced by substituents such as COOH, SO₃H, NH₂, F,Cl, Br, I, OH, SH, epoxy, isocyanate, silicone, lower alkyl esters andlower alkyl ethers; also, R₃ and R₄ can be combined to form a bicyclicring; and x, y and z are the relative percentages of each co-monomer. Xcan range from about 1 to about 100 percent or more preferably from 1 to70 percent and most preferred, from about 1 to about 50 percent. Y canbe from about 99 to about 0 percent, preferably, from about 9 to about30 percent, or most preferably, about 9 to about 50 percent. Z can rangefrom about 0 to about 50 percent. One of ordinary skill in the art wouldalso understand that if an acid group is selected as a ligand in theabove structure that it too could be neutralized with the organic fattyacids described above.

The HNP's of the present invention may also be blended with highcrystalline acid copolymers and their ionomer derivatives (which may beneutralized with conventional metal cations or the organic fatty acidsand salts thereof) or a blend of a high crystalline acid copolymer andits ionomer derivatives and at least one additional material, preferablyan acid copolymer and its ionomer derivatives. As used herein, the term“high crystalline acid copolymer” is defined as a “product-by-process”in which an acid copolymer or its ionomer derivatives formed from aethylene/carboxylic acid copolymer comprising about 5 to about 35percent by weight acrylic or methacrylic acid, wherein the copolymer ispolymerized at a temperature of about 130° C. to 200° C., at pressuresgreater than about 20,000 psi preferably greater than about 25,000 psi,more pref. from about 25,000 psi to about 50,000 psi, wherein up toabout 70 percent, preferably 100 percent, of the acid groups areneutralized with a metal ion, organic fatty acids and salts thereof, ora mixture thereof. The copolymer can have a melt index (“MI”) of fromabout 20 to about 300 g/10 min, preferably about 20 to about 200 g/10min, and upon neutralization of the copolymer, the resulting acidcopolymer and its ionomer derivatives should have an MI of from about0.1 to about 30.0 g/10 min.

Suitable high crystalline acid copolymer and its ionomer derivativescompositions and methods for making them are disclosed in U.S. Pat. No.5,580,927, the disclosure of which is hereby incorporated by referencein its entirety.

The high crystalline acid copolymer or its ionomer derivatives employedin the present invention are preferably formed from a copolymercontaining about 5 to about 35 percent, more preferably from about 9 toabout 18, most preferably about 10 to about 13 percent, by weight ofacrylic acid, wherein up to about 75 percent, most preferably about 60percent, of the acid groups are neutralized with an organic fatty acid,salt thereof, or a metal ion, such as sodium, lithium, magnesium, orzinc ion.

Generally speaking, high crystalline acid copolymer and its ionomerderivatives are formed by polymerization of their base copolymers atlower temperatures, but at equivalent pressures to those used forforming a conventional acid copolymer and its ionomer derivatives.Conventional acid copolymers are typically polymerized at apolymerization temperature of from at least about 200° C. to about 270°C., preferably about 220° C., and at pressures of from about 23,000 toabout 30,000 psi. In comparison, the high crystalline acid copolymer andits ionomer derivatives employed in the present invention are producedfrom acid copolymers that are polymerized at a polymerizationtemperature of less than 200° C., and preferably from about 130° C. toabout 200° C., and at pressures from about 20,000 to about 50,000 psi.

The HNP's may also be blended with cationic ionomers, such as thosedisclosed in U.S. Pat. No. 6,193,619 which is incorporated herein byreference. In particular, cationic ionomers have a structure accordingto the formula:

or the formula:

wherein R₁-R₉ are organic moieties of linear or branched chain alkyl,carbocyclic, or aryl; and Z is the negatively charged conjugate ionproduced following alkylation and/or quaternization. The cationicpolymers may also be quarternized up to 100% by the organic fatty acidsdescribed above.

In addition, such alkyl group may also contain various substituents inwhich one or more hydrogen atoms has been replaced by a functionalgroup. Functional groups include but are not limited to hydroxyl, amino,carboxyl, amide, ester, ether, sulfonic, siloxane, siloxyl, silanes,sulfonyl, and halogen.

As used herein, substituted and unsubstituted carbocyclic groups of upto about 20 carbon atoms means cyclic carbon-containing compounds,including but not limited to cyclopentyl, cyclohexyl, cycloheptyl, andthe like. Such cyclic groups may also contain various substituents inwhich one or more hydrogen atoms has been replaced by a functionalgroup. Such functional groups include those described above, and loweralkyl groups as described above. The cyclic groups of the invention mayfurther comprise a heteroatom.

The HNP's may also be blended with polyurethane and polyurea ionomerswhich include anionic moieties or groups, such as those disclosed inU.S. Pat. No. 6,207,784 which is incorporated herein by reference.Typically, such groups are incorporated onto the diisocyanate ordiisocyanate component of the polyurethane or polyurea ionomers. Theanionic group can also be attached to the polyol or amine component ofthe polyurethane or polyurea, respectively. Preferably, the anionicgroup is based on a sulfonic, carboxylic or phosphoric acid group. Also,more than one type of anionic group can be incorporated into thepolyurethane or polyurea. Examples of anionic polyurethane ionomers withanionic groups attached to the diisocyanate moiety can have a chemicalstructure according to the following formula:

where A=R-Z⁻M^(+x); R is a straight chain or branched aliphatic group, asubstituted straight chain or branched aliphatic group, or an aromaticor substituted aromatic group; Z=SO₃ ⁻, CO₂ ⁻ or HPO₃ ⁻; M is a groupIA, IB, IIA, IIB, IIIA, IIIB, IVA, IVB, VA, VB, VIA, VIB, VIIB or VIIIBmetal; x=1 to 5; B is a straight chain or branched aliphatic group, asubstituted straight chain or branched aliphatic group, or an aromaticor substituted aromatic group; and n=1 to 100. Preferably, M^(+x) is oneof the following: Li⁺, Na⁺, K⁺, Mg⁺², Zn⁺², Ca⁺², Mn⁺², Al⁺³, Ti^(+x),Zr^(+x), W^(+x) or Hf^(+x).

Exemplary anionic polyurethane ionomers with anionic groups attached tothe polyol component of the polyurethane are characterized by the abovechemical structure where A is a straight chain or branched aliphaticgroup, a substituted straight chain or branched aliphatic group, or anaromatic or substituted aromatic group; B═R-Z⁻M^(+x); R is a straightchain or branched aliphatic group, a substituted straight chain orbranched aliphatic group, or an aromatic or substituted aromatic group;Z=SO₃ ⁻, CO₂ ⁻ or HPO₃ ⁻; M is a group IA, IB, IIA, IIB, IIIA, IIIB,IVA, IVB, VA, VB, VIA, VIB, VIIB or VIIIB metal; x=1 to 5; and n=1 to100. Preferably, M^(+x) is one of the following: Li⁺, Na⁺, K⁺, Mg⁺²,Zn⁺², Ca⁺², Mn⁺², Al⁺³, Ti^(+x), Zr^(+x), W^(+x) or Hf^(+x).

Examples of suitable anionic polyurea ionomers with anionic groupsattached to the diisocyanate component have a chemical structureaccording to the following chemical structure:

where A=R-Z⁻M^(+x); R is a straight chain or branched aliphatic group, asubstituted straight chain or branched aliphatic group, or an aromaticor substituted aromatic group; Z=SO₃ ⁻, CO₂ ⁻ or HPO₃ ⁻; M is a groupIA, IB, IIA, IIB, IIIA, IIIB, IVA, IVB, VA, VB, VIA, VIB, VIIB or VIIIBmetal; x=1 to 5; and B is a straight chain or branched aliphatic group,a substituted straight chain or branched aliphatic group, or an aromaticor substituted aromatic group. Preferably, M^(+x) is one of thefollowing: Li⁺, Na⁺, K⁺, Mg⁺², Zn⁺², Ca⁺², Mn⁺², Al⁺³, Ti^(+x), Zr^(+x),W^(+x) or Hf^(+x).

Suitable anionic polyurea ionomers with anionic groups attached to theamine component of the polyurea are characterized by the above chemicalstructure where A is a straight chain or branched aliphatic group, asubstituted straight chain or branched aliphatic group, or an aromaticor substituted aromatic group; B═R-Z⁻M^(+X); R is a straight chain orbranched aliphatic group, a substituted straight chain or branchedaliphatic group, or an aromatic or substituted aromatic group; Z=SO₃ ⁻,CO₂ ⁻, or HPO₃ ⁻; M is a group IA, IB, IIA, IIB, IIIA, IIIB, IVA, IVB,VA, VB, VIA, VIB, VIIB or VIIIB metal; and x=1 to 5. Preferably, M^(+x)is one of the following: Li⁺, Na⁺, K⁺, Mg⁺², Zn⁺², Ca⁺², Mn⁺², Al⁺³,Ti^(+x), Zr^(+x), W^(+x), or Hf^(+x). The anionic polyurethane andpolyurea ionomers may also be neutralized up to 100% by the organicfatty acids described above.

The anionic polymers useful in the present invention, such as thosedisclosed in U.S. Pat. No. 6,221,960 which is incorporated herein byreference, include any homopolymer, copolymer or terpolymer havingneutralizable hydroxyl and/or dealkylable ether groups, and in which atleast a portion of the neutralizable or dealkylable groups areneutralized or dealkylated with a metal ion.

As used herein “neutralizable” or “dealkylable” groups refer to ahydroxyl or ether group pendent from the polymer chain and capable ofbeing neutralized or dealkylated by a metal ion, preferably a metal ionbase. These neutralized polymers have improved properties critical togolf ball performance, such as resiliency, impact strength and toughnessand abrasion resistance. Suitable metal bases are ionic compoundscomprising a metal cation and a basic anion. Examples of such basesinclude hydroxides, carbonates, acetates, oxides, sulfides, and thelike.

The particular base to be used depends upon the nature of the hydroxylor ether compound to be neutralized or dealkylated, and is readilydetermined by one skilled in the art. Preferred anionic bases includehydroxides, carbonates, oxides and acetates.

The metal ion can be any metal ion which forms an ionic compound withthe anionic base. The metal is not particularly limited, and includesalkali metals, preferably lithium, sodium or potassium; alkaline earthmetals, preferably magnesium or calcium; transition metals, preferablytitanium, zirconium, or zinc; and Group III and IV metals. The metal ioncan have a +1 to +5 charge. Most preferably, the metal is lithium,sodium, potassium, zinc, magnesium, titanium, tungsten, or calcium, andthe base is hydroxide, carbonate or acetate.

The anionic polymers useful in the present invention include those whichcontain neutralizable hydroxyl and/or dealkylable ether groups.Exemplary polymers include ethylene vinyl alcohol copolymers, polyvinylalcohol, polyvinyl acetate, poly(p-hydroxymethylene styrene), andp-methoxy styrene, to name but a few. It will be apparent to one skilledin the art that many such polymers exist and thus can be used in thecompositions of the invention. In general, the anionic polymer can bedescribed by the chemical structure:

where R₁ is OH, OC(O)R_(a), O-M^(+V), (CH₂)_(n)R_(b),(CHR_(z))_(n)R_(b), or aryl, wherein n is at least 1, R_(a) is a loweralkyl, M is a metal ion, V is an integer from 1 to 5, R_(b) is OH,OC(O)R_(a), O-M^(+V), and R_(z) is a lower alkyl or aryl, and R₂, R₃ andR₄ are each independently hydrogen, straight-chain or branched-chainlower alkyl. R₂, R₃ and R₄ may also be similarly substituted. Preferablyn is from 1 to 12, more preferably 1 to 4.

The term “substituted,” as used herein, means one or more hydrogen atomshas been replaced by a functional group. Functional groups include, butare not limited to, hydroxyl, amino, carboxyl, sulfonic, amide, ether,ether, phosphates, thiol, nitro, silane, and halogen, as well as manyothers which are quite familiar to those of ordinary skill in this art.

The terms “alkyl” or “lower alkyl,” as used herein, includes a group offrom about 1 to 30 carbon atoms, preferably 1 to 10 carbon atoms.

In the anionic polymers useful in the present invention, at least aportion of the neutralizable or dealkylable groups of R₁ are neutralizedor dealkylated by an organic fatty acid, a salt thereof, a metal base,or a mixture thereof to form the corresponding anionic moiety. Theportion of the neutralizable or dealkylable groups which are neutralizedor dealkylated can be between about 1 to about 100 weight percent,preferably between about 50 to about 100 weight percent, more preferablybefore about 90 to about 100.

Neutralization or dealkylation may be performed by melting the polymerfirst, then adding a metal ion in an extruder. The degree ofneutralization or dealkylation is controlled by varying the amount ofmetal ion added. Any method of neutralization or dealkylation availableto those of ordinary skill in the art may also be suitably employed.

In one embodiment, the anionic polymer is repeating units any one of thethree homopolymer units in the chemical structure above. In a preferredembodiment, R₂, R₃ and R₄ are hydrogen, and R₁ is hydroxyl, i.e., theanionic polymer is a polyvinyl alcohol homopolymer in which a portion ofthe hydroxyl groups have been neutralized with a metal base. In anotherpreferred embodiment, R₂, R₃ and R₄ are hydrogen, R₁ is OC(O)R_(a), andR_(a) is methyl, i.e., the anionic polymer is a polyvinyl acetatehomopolymer in which a portion of the methyl ether groups have beendealkylated with a metal ion.

The anionic polymer can also be a copolymer of two different repeatingunits having different substituents, or a terpolymer of three differentrepeating units described in the above formula. In this embodiment, thepolymer can be a random copolymer, an alternating copolymer, or a blockcopolymer, where the term “copolymer” includes terpolymers.

In another embodiment, the anionic polymer is a copolymer, wherein R₅,R₆, R₇ and R₈ are each independently selected from the group definedabove for R₂. The first unit of the copolymer can comprise from about 1to 99 percent weight percent of the polymer, preferably from about 5 to50 weight percent, and the second unit of the copolymer can comprisefrom about 99 to 1 weight percent, preferably from about 95 to 50 weightpercent. In one preferred embodiment, the anionic polymer is a random,alternating or block copolymer of units (Ia) and (Ib) wherein R₁ ishydroxyl, and each of the remaining R groups is hydrogen, i.e., thepolymer is a copolymer of ethylene and vinyl alcohol. In anotherpreferred embodiment, the anionic polymer is a random, alternating orblock copolymer of units (Ia) and (Ib) wherein R₁ is OC(O)R₅, where R₅is methyl, and each of the remaining R groups is hydrogen, i.e., thepolymer is a copolymer of ethylene and vinyl acetate.

In another embodiment, the anionic polymer is an anionic polymer havingneutralizable hydroxyl and/or dealkylable ether groups of as in theabove chemical structure wherein R₁₋₉ and R_(b) and R_(z) are as definedabove; R₁₀₋₁₁ are each independently selected from the group as definedabove for R₂; and R₁₂ is OH or OC(O)R₁₃, where R₁₃ is a lower alkyl;wherein x, y and z indicate relative weight percent of the differentunits. X can be from about 99 to about 50 weight percent of the polymer,y can be from about 1 to about 50 weight percent of the polymer, and zranges from about 0 to about 50 weight percent of the polymer. At leasta portion of the neutralizable groups R₁ are neutralized. When theamount of z is greater than zero, a portion of the groups R₁₀ can alsobe fully or partially neutralized, as desired.

In particular, the anionic polymers and blends thereof can comprisecompatible blends of anionic polymers and ionomers, such as the ionomersdescribed above, and ethylene acrylic methacrylic acid ionomers, andtheir terpolymers, sold commercially under the trade names SURLYN® andIOTEK® by DuPont and Exxon respectively. The anionic polymer blendsuseful in the golf balls of the invention can also include otherpolymers, such as polyvinylalcohol, copolymers of ethylene and vinylalcohol, poly(ethylethylene), poly(heptylethylene),poly(hexyldecylethylene), poly(isopentylethylene), poly(butylacrylate),acrylate), poly(2-ethylbutyl acrylate), poly(heptyl acrylate),poly(2-methylbutyl acrylate), poly(3-methylbutyl acrylate),poly(N-octadecylacrylamide), poly(octadecyl methacrylate),poly(butoxyethylene), poly(methoxyethylene), poly(pentyloxyethylene),poly(1,1-dichloroethylene), poly(4-[(2-butoxyethoxy)methyl]styrene),poly[oxy(ethoxymethyl)ethylene], poly(oxyethylethylene),poly(oxytetramethylene), poly(oxytrimethylene), poly(silanes) andpoly(silazanes), polyamides, polycarbonates, polyesters, styrene blockcopolymers, polyetheramides, polyurethanes, main-chain heterocyclicpolymers and poly(furan tetracarboxylic acid diimides), as well as theclasses of polymers to which they belong.

The anionic polymer compositions typically have a flexural modulus offrom about 500 psi to about 300,000 psi, preferably from about 2000 toabout 200,000 psi. The anionic polymer compositions typically have amaterial hardness of at least about 15 Shore A, preferably between about30 Shore A and 80 Shore D, more preferably between about 50 Shore A and60 Shore D. The loss tangent, or dissipation factor, is a ratio of theloss modulus over the dynamic shear storage modulus, and is typicallyless than about 1, preferably less than about 0.01, and more preferablyless than about 0.001 for the anionic polymer compositions measured atabout 23° C. The specific gravity is typically greater than about 0.7,preferably greater than about 1, for the anionic polymer compositions.The dynamic shear storage modulus, or storage modulus, of the anionicpolymer compositions at about 23° C. is typically at least about 10,000dyn/cm².

The materials used in forming either the golf ball center or any portionof the core, in accordance with the invention, may be combined to form amixture by any type of mixing known to one of ordinary skill in the art.Suitable types of mixing include single pass and multi-pass mixing.Suitable mixing equipment is well known to those of ordinary skill inthe art, and such equipment may include a Banbury mixer, a two-rollmill, or a twin screw extruder.

Conventional mixing speeds for combining polymers are typically used.The mixing temperature depends upon the type of polymer components, andmore importantly, on the type of free-radical initiator. Suitable mixingspeeds and temperatures are well-known to those of ordinary skill in theart, or may be readily determined without undue experimentation. Themixture can be subjected to, e.g., a compression or injection moldingprocess, to obtain solid spheres for the center or hemispherical shellsfor forming an intermediate layer. The temperature and duration of themolding cycle are selected based upon reactivity of the mixture. Themolding cycle may have a single step of molding the mixture at a singletemperature for a fixed time duration. The molding cycle may alsoinclude a two-step process, in which the polymer mixture is held in themold at an initial temperature for an initial duration of time, followedby holding at a second, typically higher temperature for a secondduration of time. In a preferred embodiment of the current invention, asingle-step cure cycle is employed. The materials used in forming eitherthe golf ball center or any portion of the core, in accordance with theinvention, may be combined to form a golf ball by an injection moldingprocess, which is also well-known to one of ordinary skill in the art.Although the curing time depends on the various materials selected,those of ordinary skill in the art will be readily able to adjust thecuring time upward or downward based on the particular materials usedand the discussion herein.

Thermoplastic resins and rubbers for use as the matrix polymer and/or asan intercalant polymer, in the practice of this invention may varywidely. Illustrative of useful thermoplastic resins, which may be usedalone or in admixture, include, but are not limited to, polylactonessuch as poly(pivalolactone), poly(caprolactone) and the like;polyurethanes derived from reaction of diisocyanates such as1,5-naphthalene diisocyanate; p-phenylene diisocyanate, m-phenylenediisocyanate, 2,4-toluene diisocyanate, 4,4′-diphenylmethanediisocyanate, 3,3′-dimethyl-4,4′-diphenyl-methane diisocyanate,3,3′-dimethyl-4,4′-biphenyl diisocyanate, 4,4′-diphenylisopropylidenediisocyanate, 3,3′-dimethyl-4,4′-diphenyl diisocyanate,3,3′-dimethyl-4,4′-diphenylmethane diisocyanate,3,3′-dimethoxy-4,4′-biphenyl diisocyanate, dianisidine diisocyanate,toluidine diisocyanate, hexamethylene diisocyanate,4,4′-diisocyanatodiphenylmethane, and the like.

Also suitable are linear long-chain diols such as poly(tetramethyleneadipate), poly(ethylene adipate), poly(1,4-butylene adipate),poly(ethylene succinate), poly(2,3-butylene succinate), polyether diolsand the like; polycarbonates such as poly[methanebis(4-phenyl)carbonate], poly[1,1-ether bis(4-phenyl)carbonate],poly[diphenylmethane bis(4-phenyl)carbonate], poly[1,1-cyclohexanebis(4-phenyl)carbonate] and the like; polysulfones; polyethers;polyketones; polyamides such as poly(4-amino butyric acid),poly(hexamethylene adipamide), poly(6-aminohexanoic acid),poly(m-xylylene adipamide), poly(p-xylylene sebacamide),poly(2,2,2-trimethyl hexamethylene terephthalamide), poly(m-phenyleneisophthalamide) (NOMEX®), poly(p-phenylene terephthalamide) (KEVLAR®),and the like; polyesters such as poly(ethylene azelate),poly(ethylene-1,5-naphthalate, poly(1,4-cyclohexane dimethyleneterephthalate), poly(ethylene oxybenzoate) (A-TELL®), poly(p-hydroxybenzoate) (EKONOL®), poly(1,4-cyclohexylidene dimethylene terephthalate)(KODEL®), poly(1,4-cyclohexylidene dimethylene terephthalate) (KODEL®),polyethylene terephthalate, polybutylene terephthalate, polytrimethyleneterepthalate (“PTT”), and the like; poly(arylene oxides) such aspoly(2,6-dimethyl-1,4-phenylene oxide), poly(2,6-diphenyl-1,4-phenyleneoxide) and the like; poly(arylene sulfides) such as poly(phenylenesulfide), and the like.

Further suitable polymers include, but are not limited topolyetherimides; vinyl polymers and their copolymers such as polyvinylacetate, polyvinyl alcohol, polyvinyl chloride; polyvinyl butyral,polyvinylidene chloride, ethylene-vinyl acetate copolymers, and thelike; polyacrylics, polyacrylate and their copolymers such as polyethylacrylate, poly(n-butyl acrylate), polymethylmethacrylate, polyethylmethacrylate, poly(n-butyl methacrylate), poly(n-propyl methacrylate),polyacrylamide, polyacrylonitrile, polyacrylic acid, ethylene-acrylicacid copolymers, ethylene-vinyl alcohol copolymers acrylonitrilecopolymers, methyl methacrylate-styrene copolymers, ethylene-ethylacrylate copolymers, methacrylated butadiene-styrene copolymers, and thelike; polyolefins such as low density poly(ethylene), poly(propylene),chlorinated low density poly(ethylene), poly(4-methyl-1-pentene),poly(ethylene), poly(styrene), and the like; ionomers;poly(epichlorohydrins); and polysulfones, such as the reaction productof the sodium salt of 2,2-bis(4-hydroxyphenyl)propane and4,4′-dichlorodiphenyl sulfone; furan resins, such as poly(furan);cellulose ester plastics, such as cellulose acetate, cellulose acetatebutyrate, cellulose propionate, and the like; silicones such aspoly(dimethyl siloxane), poly(dimethyl siloxane), poly(dimethyl siloxaneco-phenylmethyl siloxane), and the like; protein plastics; and blends oftwo or more of the foregoing.

Preferably, the nanomaterials can be blended with materials such asionomers, copolyether-ester, copolyester-ester, copolyether-amide,copolyester-amide, thermoplastic urethanes, metallocene or single-sitenon-metallocene catalyzed polymers, polyamides, liquid crystal polymers,as well as other polymers mentioned in U.S. Pat. No. 6,124,389; U.S.Pat. No 6,025,442; and U.S. Pat. No 6,001,930, the disclosure of whichare incorporated herein, in their entirety, by express referencethereto.

Vulcanizable and thermoplastic rubbers useful as the matrix polymerand/or as a water insoluble intercalant polymer, in the practice of thisinvention may also vary widely. Examples include but are not limited to,brominated butyl rubber, chlorinate butyl rubber, polyurethaneelastomers, fluoroelastomers, polyester elastomers, polyvinylchloride,butadiene/acrylonitrile elastomers, silicone elastomers,poly(butadiene), poly(isoprene), poly(isobutylene), ethylene-propylenecopolymers, ethylene-propylene-diene terpolymers, sulfonatedethylene-propylene-diene terpolymers, poly(chloroprene),poly(2,3-dimethylbutadiene), poly(butadiene-pentadiene),chlorosulphonated poly(ethylenes), poly(sulfide) elastomers, blockcopolymers made up of segments of glassy or crystalline blocks such aspoly(styrene), poly(vinyltoluene), poly(t-butyl styrene), polyesters andthe like and the elastomeric blocks such as poly(butadiene),poly(isoprene), ethylene-propylene copolymers, ethylene-butylenecopolymers, polyether and the like as for example the copolymers inpoly(styrene)-poly(butadiene)-poly(styrene) block copolymer manufacturedby Shell Chemical Company of Houston, Tex., under the trade nameKRATON®.

Useful thermosetting resins include, but are not limited to, polyamides;polyalkylamides; polyesters; polyurethanes; polycarbonates;polyepoxides; and mixtures thereof. Thermoset resins based onwater-soluble prepolymers, include prepolymers based on formaldehyde:phenols (phenol, cresol and the like); urea; melamine; melamine andphenol; urea and phenol. Polyurethanes based on: toluene diisocyanate(“TDI”) and monomeric and polymeric diphenyl methanediisocyanates(“MDI”), p-phenylenediisocynate (“PPDI”); hydroxy terminated polyethers(polyethylene glycol, polypropylene glycol, copolymers of ethylene oxideand propylene oxide and the like); amino terminated polyethers,polyamines (tetramethylene diamine, ethylenediamine,hexamethylenediamine, 2,2-dimethyl 1,3-propanediamine; melamine,diaminobenzene, triaminobenzene and the like); polyamidoamines (forinstance, hydroxy terminated polyesters); unsaturated polyesters basedon maleic and fumaric anhydrides and acids; glycols (ethylene,propylene), polyethylene glycols, polypropylene glycols, aromaticglycols and polyglycols; unsaturated polyesters based on vinyl, allyland acryl monomers; epoxides, based on biphenol A(2,2′-bis(4-hydroxyphenyl)propane) and epichlorohydrin; epoxyprepolymers based on monoepoxy and polyepoxy compounds andα,β-unsaturated compounds (styrene, vinyl, allyl, acrylic monomers);polyamides 4-tetramethylene diamine, hexamethylene diamine, melamine,1,3-propanediamine, diaminobenzene, triaminobenzene,3,3′,4,4′-bitriaminobenzene; 3,3′,4,4′-biphenyltetramine and the like).

Also suitable are polyethyleneimines; amides and polyamides (amides ofdi-, tri-, and tetra acids); hydroxyphenols (pyrogallol, gallic acid,tetrahydroxybenzophenone, tetrahydroquinone, catechol, phenol and thelike); anhydrides and polyandrides of di-, tri-, and tetraacids;polyisocyanurates based on TDI and MDI; polyimides based on pyromelliticdianhydride and 1,4-phenyldiamine; polybenzimidozoles based on33′,44′-biphenyltetramine and isophthalic acid; polyamide based onunsaturated dibasic acids and anhydrides (maleic, fumaric) and aromaticpolyamides; alkyd resins based on dibasic aromatic acids or anhydrides,glycerol, trimethylolpropane, pentaerythritol, sorbitol and unsaturatedfatty long chain carboxylic acids (the latter derived from vegetableoils); and prepolymers based on acrylic monomers (hydroxy or carboxyfunctional).

In addition, the nanoparticulates can be incorporated in thepolyurethane, polyurea and epoxy and their ionomeric derivatives and IPNpolymers that are known in the golf ball compositions. This can beachieved by various processes like casting, reaction injection moldingand other process that are well known in the art. Further, thenanomaterials can also be used in ink and paint formulations to improveits mechanical properties and abrasion resistant. The nanomaterials canbe present any where between about 0.5 and about 20 weight percent inthe compositions of the present invention.

In a preferred embodiment of the present invention, the polymercomposition, typically a polybutadiene rubber based rubber composition,comprises nanoparticulate zinc oxide, which has an average particlediameter of less than 100 nm. Conventional ZnO ranges in size from about1 μm to about 50 μm. Without wishing to be bound by any particulartheory it is believed that the smaller particle size of thenanoparticulate ZnO, which has a much larger active surface area thandoes convention ZnO, allows the ZnO nanoparticles to “participate” moreintricately in the formation and development of the polybutadieneproperties. An example of nanoparticulate ZnO includes NANOX®, which iscommercially available from Elementis of Gent, Belgium. Properties ofNANOX® are presented in tabular form below:

Property Value Surface Area (BET) 17 m2/g Average Particle Size 60 nmZinc Oxide 99.0% Loss on Ignition 1.0% max Iron <100 ppm Lead <50 ppmArsenic <5 ppm Cadmium <10 ppm

Other non-reacting, high-specific nanoparticulates that are suitable forthe blends of the present invention include tungsten, tungsten trioxide,tungsten carbide, bismuth trioxide, tin oxide, nickel, aluminum oxide,iron oxide, and mixtures thereof.

The cover provides the interface between the ball and a club. Propertiesthat are desirable for the cover include good moldability, high abrasionresistance, high tear strength, high resilience, and good mold release.The cover typically has a thickness to provide sufficient strength, goodperformance characteristics, and durability. The cover preferably has athickness of less than about 0.1 inches, preferably, less than about0.05 inches, more preferably, between about 0.02 inches and about 0.04inches, and most preferably, between about 0.025 and about 0.035 inches.The invention is particularly directed towards a multilayer golf ballwhich comprises a core, an inner cover layer, and an outer cover layer.In this embodiment, preferably, at least one of the inner and outercover layer has a thickness of less than about 0.05 inches, morepreferably between about 0.02 inches and about 0.04 inches. Mostpreferably, the thickness of either layer is about 0.03 inches.

When the golf ball of the present invention includes an intermediatelayer, such as an outer core layer or an inner cover layer, any or allof these layer(s) may comprise thermoplastic and thermosetting material,but preferably the intermediate layer(s), if present, comprise anysuitable material, such as ionic copolymers of ethylene and anunsaturated monocarboxylic acid which are available under the trademarkSURLYN® of E.I. DuPont de Nemours & Co., of Wilmington, Del., or IOTEK®or ESCOR® of Exxon. These are copolymers or terpolymers of ethylene andmethacrylic acid or acrylic acid partially neutralized with salts ofzinc, sodium, lithium, magnesium, potassium, calcium, manganese, nickelor the like, in which the salts are the reaction product of an olefinhaving from 2 to 8 carbon atoms and an unsaturated monocarboxylic acidhaving 3 to 8 carbon atoms. The carboxylic acid groups of the copolymermay be totally or partially neutralized and might include methacrylic,crotonic, maleic, fumaric or itaconic acid.

PPPPThe golf balls of the present invention can likewise include one ormore homopolymeric or copolymeric inner or outer cover materials, suchas:

-   -   (1) Vinyl resins, such as those formed by the polymerization of        vinyl chloride, or by the copolymerization of vinyl chloride        with vinyl acetate, acrylic esters or vinylidene chloride;    -   (2) Polyolefins, such as polyethylene, polypropylene,        polybutylene and copolymers such as ethylene methylacrylate,        ethylene ethylacrylate, ethylene vinyl acetate, ethylene        methacrylic or ethylene acrylic acid or propylene acrylic acid        and copolymers and homopolymers produced using a single-site        catalyst or a metallocene catalyst;    -   (3) Polyurethanes, such as those prepared from polyols and        diisocyanates or polyisocyanates, in particular PPDI-based        thermoplastic polyurethanes, and those disclosed in U.S. Pat.        No. 5,334,673;    -   (4) Polyureas, such as those disclosed in U.S. Pat. No.        5,484,870;    -   (5) Polyamides, such as poly(hexamethylene adipamide) and others        prepared from diamines and dibasic acids, as well as those from        amino acids such as poly(caprolactam), and blends of polyamides        with SURLYN®, polyethylene, ethylene copolymers,        ethylene-propylene-non-conjugated diene terpolymer, and the        like;    -   (6) Acrylic resins and blends of these resins with poly vinyl        chloride, elastomers, and the like;    -   (7) Thermoplastics, such as urethane; olefinic thermoplastic        rubbers, such as blends of polyolefins with        ethylene-propylene-non-conjugated diene terpolymer; block        copolymers of styrene and butadiene, isoprene or        ethylene-butylene rubber; or copoly(ether-amide), such as        PEBAX®, sold by ELF Atochem of Philadelphia, Pa.;    -   (8) Polyphenylene oxide resins or blends of polyphenylene oxide        with high impact polystyrene as sold under the trademark NORYL®        by General Electric Company of Pittsfield, Mass.;    -   (9) Thermoplastic polyesters, such as polyethylene        terephthalate, polybutylene terephthalate, polyethylene        terephthalate/glycol modified, poly(trimethylene terepthalate),        and elastomers sold under the trademarks HYTREL® by E.I. DuPont        de Nemours & Co. of Wilmington, Del., and LOMOD® by General        Electric Company of Pittsfield, Mass.;    -   (10) Blends and alloys, including polycarbonate with        acrylonitrile butadiene styrene, polybutylene terephthalate,        polyethylene terephthalate, styrene maleic anhydride,        polyethylene, elastomers, and the like, and polyvinyl chloride        with acrylonitrile butadiene styrene or ethylene vinyl acetate        or other elastomers; and    -   (11) Blends of thermoplastic rubbers with polyethylene,        propylene, polyacetal, nylon, polyesters, cellulose esters, and        the like.

Preferably, the inner and/or outer covers include polymers, such asethylene, propylene, butene-1 or hexane-1 based homopolymers orcopolymers including functional monomers, such as acrylic andmethacrylic acid and fully or partially neutralized ionomer resins andtheir blends, methyl acrylate, methyl methacrylate homopolymers andcopolymers, imidized, amino group containing polymers, polycarbonate,reinforced polyamides, polyphenylene oxide, high impact polystyrene,polyether ketone, polysulfone, poly(phenylene sulfide),acrylonitrile-butadiene, acrylic-styrene-acrylonitrile, poly(ethyleneterephthalate), poly(butylene terephthalate), poly(vinyl alcohol),poly(tetrafluoroethylene) and their copolymers including functionalcomonomers, and blends thereof. Suitable layer compositions also includea polyether or polyester thermoplastic urethane, a thermosetpolyurethane, a low modulus ionomer, such as acid-containing ethylenecopolymer ionomers, including E/X/Y terpolymers where E is ethylene, Xis an acrylate or methacrylate-based softening comonomer present inabout 0 to 50 weight percent and Y is acrylic or methacrylic acidpresent in about 5 to 35 weight percent. More preferably, in a low spinrate embodiment designed for maximum distance, the acrylic ormethacrylic acid is present in about 16 to 35 weight percent, making theionomer a high modulus ionomer. In a higher spin embodiment, the innercover layer includes an ionomer where an acid is present in about 10 to15 weight percent and includes a softening comonomer. Additionally,high-density polyethylene (“HDPE”), low-density polyethylene (“LDPE”),LLDPE, and homo- and co-polymers of polyolefin are suitable for avariety of golf ball layers.

While also suitable for intermediate layers, in one embodiment, theouter cover preferably includes a polyurethane composition comprisingthe reaction product of at least one polyisocyanate, polyol, and atleast one curing agent. Any polyisocyanate available to one of ordinaryskill in the art is suitable for use according to the invention.Exemplary polyisocyanates include, but are not limited to,4,4′-diphenylmethane diisocyanate (“MDI”); polymeric MDI;carbodiimide-modified liquid MDI; 4,4′-dicyclohexylmethane diisocyanate(“H₁₂MDI”); p-phenylene diisocyanate (“PPDI”); m-phenylene diisocyanate(“MPDI”); toluene diisocyanate (“TDI”); 3,3′-dimethyl-4,4′-biphenylenediisocyanate (“TODI”); isophoronediisocyanate (“IPDI”); hexamethylenediisocyanate (“HDI”); naphthalene diisocyanate (“NDI”); xylenediisocyanate (“XDI”); p-tetramethylxylene diisocyanate (“p-TMXDI”);m-tetramethylxylene diisocyanate (“m-TMXDI”); ethylene diisocyanate;propylene-1,2-diisocyanate; tetramethylene-1,4-diisocyanate; cyclohexyldiisocyanate; 1,6-hexamethylene-diisocyanate (“HDI”);dodecane-1,12-diisocyanate; cyclobutane-1,3-diisocyanate;cyclohexane-1,3-diisocyanate; cyclohexane-1,4-diisocyanate;1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane; methylcyclohexylene diisocyanate; triisocyanate of HDI; triisocyanate of2,4,4-trimethyl-1,6-hexane diisocyanate (“TMDI”); tetracenediisocyanate; napthalene diisocyanate; anthracene diisocyanate;isocyanurate of toluene diisocyanate; uretdione of hexamethylenediisocyanate; and mixtures thereof. Polyisocyanates are known to thoseof ordinary skill in the art as having more than one isocyanate group,e.g., di-isocyanate, tri-isocyanate, and tetra-isocyanate. Preferably,the polyisocyanate includes MDI, PPDI, TDI, or a mixture thereof, andmore preferably, the polyisocyanate includes MDI. It should beunderstood that, as used herein, the term “MDI” includes4,4′-diphenylmethane diisocyanate, polymeric MDI, carbodiimide-modifiedliquid MDI, and mixtures thereof and, additionally, that thediisocyanate employed may be “low free monomer,” understood by one ofordinary skill in the art to have lower levels of “free” monomerisocyanate groups, typically less than about 0.1% free monomer groups.Examples of “low free monomer” diisocyanates include, but are notlimited to Low Free Monomer MDI, Low Free Monomer TDI, and Low FreeMonomer PPDI.

The at least one polyisocyanate should have less than about 14%unreacted NCO groups. Preferably, the at least one polyisocyanate has nogreater than about 7.5% NCO, and more preferably, less than about 7.0%.

Any polyol available to one of ordinary skill in the art is suitable foruse according to the invention. Exemplary polyols include, but are notlimited to, polyether polyols, hydroxy-terminated polybutadiene(including partially/fully hydrogenated derivatives), polyester polyols,polycaprolactone polyols, and polycarbonate polyols. In one preferredembodiment, the polyol includes polyether polyol. Examples include, butare not limited to, polytetramethylene ether glycol (“PTMEG”),polyethylene propylene glycol, polyoxypropylene glycol, and mixturesthereof. The hydrocarbon chain can have saturated or unsaturated bondsand substituted or unsubstituted aromatic and cyclic groups. Preferably,the polyol of the present invention includes PTMEG.

In another embodiment, polyester polyols are included in thepolyurethane material of the invention. Suitable polyester polyolsinclude, but are not limited to, polyethylene adipate glycol;polybutylene adipate glycol; polyethylene propylene adipate glycol;o-phthalate-1,6-hexanediol; poly(hexamethylene adipate) glycol; andmixtures thereof. The hydrocarbon chain can have saturated orunsaturated bonds, or substituted or unsubstituted aromatic and cyclicgroups.

In another embodiment, polycaprolactone polyols are included in thematerials of the invention. Suitable polycaprolactone polyols include,but are not limited to, 1,6-hexanediol-initiated polycaprolactone,diethylene glycol initiated polycaprolactone, trimethylol propaneinitiated polycaprolactone, neopentyl glycol initiated polycaprolactone,1,4-butanediol-initiated polycaprolactone, and mixtures thereof. Thehydrocarbon chain can have saturated or unsaturated bonds, orsubstituted or unsubstituted aromatic and cyclic groups.

In yet another embodiment, the polycarbonate polyols are included in thepolyurethane material of the invention. Suitable polycarbonates include,but are not limited to, polyphthalate carbonate and poly(hexamethylenecarbonate) glycol. The hydrocarbon chain can have saturated orunsaturated bonds, or substituted or unsubstituted aromatic and cyclicgroups. In one embodiment, the molecular weight of the polyol is fromabout 200 to about 4000.

Polyamine curatives are also suitable for use in the polyurethanecomposition of the invention and have been found to improve cut, shear,and impact resistance of the resultant balls. Preferred polyaminecuratives include, but are not limited to,3,5-dimethylthio-2,4-toluenediamine and isomers thereof;3,5-diethyltoluene-2,4-diamine and isomers thereof, such as3,5-diethyltoluene-2,6-diamine;4,4′-bis-(sec-butylamino)-diphenylmethane;1,4-bis-(sec-butylamino)-benzene, 4,4′-methylene-bis-(2-chloroaniline);4,4′-methylene-bis-(3-chloro-2,6-diethylaniline) (“MCDEA”);polytetramethyleneoxide-di-p-aminobenzoate; N,N′-dialkyldiamino diphenylmethane; p,p′-methylene dianiline (“MDA”); m-phenylenediamine (“MPDA”);4,4′-methylene-bis-(2-chloroaniline) (“MOCA”);4,4′-methylene-bis-(2,6-diethylaniline) (“MDEA”);4,4′-methylene-bis-(2,3-dichloroaniline) (“MDCA”);4,4′-diamino-3,3′-diethyl-5,5′-dimethyl diphenylmethane;2,2′,3,3′-tetrachloro diamino diphenylmethane; trimethylene glycoldi-p-aminobenzoate; and mixtures thereof. Preferably, the curing agentof the present invention includes 3,5-dimethylthio-2,4-toluenediamineand isomers thereof, such as ETHACURE® 300, commercially available fromAlbermarle Corporation of Baton Rouge, La. Suitable polyamine curatives,which include both primary and secondary amines, preferably havemolecular weights ranging from about 64 to about 2000.

At least one of a diol, triol, tetraol, or hydroxy-terminated curativesmay be added to the aforementioned polyurethane composition. Suitablediol, triol, and tetraol groups include ethylene glycol; diethyleneglycol; polyethylene glycol; propylene glycol; polypropylene glycol;lower molecular weight polytetramethylene ether glycol;1,3-bis(2-hydroxyethoxy) benzene; 1,3-bis-[2-(2-hydroxyethoxy)ethoxy]benzene; 1,3-bis-{2-[2-(2-hydroxyethoxy) ethoxy]ethoxy}benzene;1,4-butanediol; 1,5-pentanediol; 1,6-hexanediol;resorcinol-di-(β-hydroxyethyl) ether; hydroquinone-di-(β-hydroxyethyl)ether; and mixtures thereof. Preferred hydroxy-terminated curativesinclude 1,3-bis(2-hydroxyethoxy) benzene; 1,3-bis-[2-(2-hydroxyethoxy)ethoxy]benzene; 1,3-bis-{2-[2-(2-hydroxyethoxy) ethoxy]ethoxy}benzene;1,4-butanediol, and mixtures thereof. Preferably, the hydroxy-terminatedcuratives have molecular weights ranging from about 48 to 2000. Itshould be understood that molecular weight, as used herein, is theabsolute weight average molecular weight and would be understood as suchby one of ordinary skill in the art.

Both the hydroxy-terminated and amine curatives can include one or moresaturated, unsaturated, aromatic, and cyclic groups. Additionally, thehydroxy-terminated and amine curatives can include one or more halogengroups. The polyurethane composition can be formed with a blend ormixture of curing agents. If desired, however, the polyurethanecomposition may be formed with a single curing agent.

In a preferred embodiment of the present invention, saturatedpolyurethanes used to form cover layers, preferably the outer coverlayer, and may be selected from among both castable thermoset andthermoplastic polyurethanes.

In this embodiment, the saturated polyurethanes of the present inventionare substantially free of aromatic groups or moieties. Saturatedpolyurethanes suitable for use in the invention are a product of areaction between at least one polyurethane prepolymer and at least onesaturated curing agent. The polyurethane prepolymer is a product formedby a reaction between at least one saturated polyol and at least onesaturated diisocyanate. As is well known in the art, a catalyst may beemployed to promote the reaction between the curing agent and theisocyanate and polyol.

Saturated diisocyanates which can be used include, without limitation,ethylene diisocyanate; propylene-1,2-diisocyanate;tetramethylene-1,4-diisocyanate; 1,6-hexamethylene-diisocyanate (“HDI”);2,2,4-trimethylhexamethylene diisocyanate; 2,4,4-trimethylhexamethylenediisocyanate; dodecane-1,12-diisocyanate; dicyclohexylmethanediisocyanate; cyclobutane-1,3-diisocyanate;cyclohexane-1,3-diisocyanate; cyclohexane-1,4-diisocyanate;1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane; isophoronediisocyanate (“IPDI”); methyl cyclohexylene diisocyanate; triisocyanateof HDI; triisocyanate of 2,2,4-trimethyl-1,6-hexane diisocyanate(“TMDI”). The most preferred saturated diisocyanates are4,4′-dicyclohexylmethane diisocyanate (“HMDI”) and isophoronediisocyanate (“IPDI”).

Saturated polyols which are appropriate for use in this inventioninclude without limitation polyether polyols such as polytetramethyleneether glycol and poly(oxypropylene) glycol. Suitable saturated polyesterpolyols include polyethylene adipate glycol, polyethylene propyleneadipate glycol, polybutylene adipate glycol, polycarbonate polyol andethylene oxide-capped polyoxypropylene diols. Saturated polycaprolactonepolyols which are useful in the invention include diethyleneglycol-initiated polycaprolactone, 1,4-butanediol-initiatedpolycaprolactone, 1,6-hexanediol-initiated polycaprolactone; trimethylolpropane-initiated polycaprolactone, neopentyl glycol initiatedpolycaprolactone, and polytetramethylene ether glycol-initiatedpolycaprolactone. The most preferred saturated polyols arepolytetramethylene ether glycol and PTMEG-initiated polycaprolactone.

Suitable saturated curatives include 1,4-butanediol, ethylene glycol,diethylene glycol, polytetramethylene ether glycol, propylene glycol;trimethanolpropane; tetra-(2-hydroxypropyl)-ethylenediamine; isomers andmixtures of isomers of cyclohexyldimethylol, isomers and mixtures ofisomers of cyclohexane bis(methylamine); triisopropanolamine; ethylenediamine; diethylene triamine; triethylene tetramine; tetraethylenepentamine; 4,4′-dicyclohexylmethane diamine;2,2,4-trimethyl-1,6-hexanediamine; 2,4,4-trimethyl-1,6-hexanediamine;diethyleneglycol di-(aminopropyl)ether;4,4′-bis-(sec-butylamino)-dicyclohexylmethane;1,2-bis-(sec-butylamino)cyclohexane; 1,4-bis-(sec-butylamino)cyclohexane; isophorone diamine; hexamethylene diamine; propylenediamine; 1-methyl-2,4-cyclohexyl diamine; 1-methyl-2,6-cyclohexyldiamine; 1,3-diaminopropane; dimethylamino propylamine; diethylaminopropylamine; imido-bis-propylamine; isomers and mixtures of isomers ofdiaminocyclohexane; monoethanolamine; diethanolamine; triethanolamine;monoisopropanolamine; and diisopropanolamine. The most preferredsaturated curatives are 1,4-butanediol, 1,4-cyclohexyldimethylol and4,4-bis-(sec-butylamino)-dicyclohexylmethane.

The compositions of the invention may also be polyurea-based, which aredistinctly different from polyurethane compositions, but also can resultin desirable aerodynamic and aesthetic characteristics when used in golfball components. The polyurea-based compositions are preferablysaturated in nature.

Without being bound to any particular theory, it is now believed thatsubstitution of the long chain polyol segment in the polyurethaneprepolymer with a long chain polyamine oligomer soft segment to form apolyurea prepolymer, improves shear, cut, and resiliency, as well asadhesion to other components. Thus, the polyurea compositions of thisinvention may be formed from the reaction product of an isocyanate andpolyamine prepolymer crosslinked with a curing agent. For example,polyurea-based compositions of the invention may be prepared from atleast one isocyanate, at least one polyether amine, and at least onediol curing agent or at least one diamine curing agent.

Any polyamine available to one of ordinary skill in the art is suitablefor use in the polyurea prepolymer. Polyether amines are particularlysuitable for use in the prepolymer. As used herein, “polyether amines”refer to at least polyoxyalkylenearnines containing primary amino groupsattached to the terminus of a polyether backbone. Due to the rapidreaction of isocyanate and amine, and the insolubility of many ureaproducts, however, the selection of diamines and polyether amines islimited to those allowing the successful formation of the polyureaprepolymers. In one embodiment, the polyether backbone is based ontetramethylene, propylene, ethylene, trimethylolpropane, glycerin, andmixtures thereof.

Suitable polyether amines include, but are not limited to,methyldiethanolamine; polyoxyalkylenediamines such as,polytetramethylene ether diamines, polyoxypropylenetriamine, andpolyoxypropylene diamines; poly(ethylene oxide capped oxypropylene)ether diamines; propylene oxide-based triamines;triethyleneglycoldiamines; trimethylolpropane-based triamines;glycerin-based triamines; and mixtures thereof. In one embodiment, thepolyether amine used to form the prepolymer is JEFFAMINE® D2000(manufactured by Huntsman Chemical Co. of Austin, Tex.).

The molecular weight of the polyether amine for use in the polyureaprepolymer may range from about 100 to about 5000. As used herein, theterm “about” is used in connection with one or more numbers or numericalranges, should be understood to refer to all such numbers, including allnumbers in a range. In one embodiment, the polyether amine molecularweight is about 200 or greater, preferably about 230 or greater. Inanother embodiment, the molecular weight of the polyether amine is about4000 or less. In yet another embodiment, the molecular weight of thepolyether amine is about 600 or greater. In still another embodiment,the molecular weight of the polyether amine is about 3000 or less. Inyet another embodiment, the molecular weight of the polyether amine isbetween about 1000 and about 3000, and more preferably is between about1500 to about 2500. Because lower molecular weight polyether amines maybe prone to forming solid polyureas, a higher molecular weight oligomer,such as Jeffamine D2000, is preferred.

In one embodiment, the polyether amine has the generic structure:

wherein the repeating unit x has a value ranging from about 1 to about70. Even more preferably, the repeating unit may be from about 5 toabout 50, and even more preferably is from about 12 to about 35.

In another embodiment, the polyether amine has the generic structure:

wherein the repeating units x and z have combined values from about 3.6to about 8 and the repeating unit y has a value ranging from about 9 toabout 50, and wherein R is —(CH₂)_(a)—, where “a” may be a repeatingunit ranging from about 1 to about 10.

In yet another embodiment, the polyether amine has the genericstructure:H₂N—(R)—O—(R)—O—(R)—N H₂wherein R is —(CH₂)_(a)—, and “a” may be a repeating unit ranging fromabout 1 to about 10.

As briefly discussed above, some amines may be unsuitable for reactionwith the isocyanate because of the rapid reaction between the twocomponents. In particular, shorter chain amines are fast reacting. Inone embodiment, however, a hindered secondary diamine may be suitablefor use in the prepolymer. Without being bound to any particular theory,it is believed that an amine with a high level of stearic hindrance,e.g., a tertiary butyl group on the nitrogen atom, has a slower reactionrate than an amine with no hindrance or a low level of hindrance. Forexample, 4,4′-bis-(sec-butylamino)-dicyclohexylmethane (CLEARLINK® 1000)may be suitable for use in combination with an isocyanate to form thepolyurea prepolymer.

Any isocyanate available to one of ordinary skill in the art is suitablefor use in the polyurea prepolymer. Isocyanates for use with the presentinvention include aliphatic, cycloaliphatic, araliphatic, aromatic, anyderivatives thereof, and combinations of these compounds having two ormore isocyanate (NCO) groups per molecule. The isocyanates may beorganic polyisocyanate-terminated prepolymers. The isocyanate-containingreactable component may also include any isocyanate-functional monomer,dimer, trimer, or multimeric adduct thereof, prepolymer,quasi-prepolymer, or mixtures thereof. Isocyanate-functional compoundsmay include monoisocyanates or polyisocyanates that include anyisocyanate functionality of two or more.

Suitable isocyanate-containing components include diisocyanates havingthe generic structure: O═C═N—R—N═C═O, where R is preferably a cyclic,aromatic, or linear or branched hydrocarbon moiety containing from about1 to about 20 carbon atoms. The diisocyanate may also contain one ormore cyclic groups or one or more phenyl groups. When multiple cyclic oraromatic groups are present, linear and/or branched hydrocarbonscontaining from about 1 to about 10 carbon atoms can be present asspacers between the cyclic or aromatic groups. In some cases, the cyclicor aromatic group(s) may be substituted at the 2-, 3-, and/or4-positions, or at the ortho-, meta-, and/or para-positions,respectively. Substituted groups may include, but are not limited to,halogens, primary, secondary, or tertiary hydrocarbon groups, or amixture thereof.

Examples of diisocyanates that can be used with the present inventioninclude, but are not limited to, substituted and isomeric mixturesincluding 2,2′-, 2,4′-, and 4,4′-diphenylmethane diisocyanate (MDI);3,3′-dimethyl-4,4′-biphenylene diisocyanate (TODI); toluene diisocyanate(TDI); polymeric MDI; carbodiimide-modified liquid 4,4′-diphenylmethanediisocyanate; para-phenylene diisocyanate (PPDI); meta-phenylenediisocyanate (MPDI); triphenyl methane-4,4′- and triphenylmethane-4,4′-triisocyanate; naphthylene-1,5-diisocyanate; 2,4′-, 4,4′-,and 2,2-biphenyl diisocyanate; polyphenyl polymethylene polyisocyanate(PMDI); mixtures of MDI and PMDI; mixtures of PMDI and TDI; ethylenediisocyanate; propylene-1,2-diisocyanate;tetramethylene-1,2-diisocyanate; tetramethylene-1,3-diisocyanate;tetramethylene-1,4-diisocyanate; 1,6-hexamethylene-diisocyanate (HDI);octamethylene diisocyanate; decamethylene diisocyanate;2,2,4-trimethylhexamethylene diisocyanate; 2,4,4-trimethylhexamethylenediisocyanate; dodecane-1,12-diisocyanate; cyclobutane-1,3-diisocyanate;cyclohexane-1,2-diisocyanate; cyclohexane-1,3-diisocyanate;cyclohexane-1,4-diisocyanate; methyl-cyclohexylene diisocyanate (HTDI);2,4-methylcyclohexane diisocyanate; 2,6-methylcyclohexane diisocyanate;4,4′-dicyclohexyl diisocyanate; 2,4′-dicyclohexyl diisocyanate;1,3,5-cyclohexane triisocyanate; isocyanatomethylcyclohexane isocyanate;1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane;isocyanatoethylcyclohexane isocyanate; bis(isocyanatomethyl)-cyclohexanediisocyanate; 4,4′-bis(isocyanatomethyl) dicyclohexane;2,4′-bis(isocyanatomethyl) dicyclohexane; isophorone diisocyanate(IPDI); triisocyanate of HDI; triisocyanate of2,2,4-trimethyl-1,6-hexane diisocyanate (TMDI); 4,4′-dicyclohexylmethanediisocyanate (H₁₂MDI); 2,4-hexahydrotoluene diisocyanate;2,6-hexahydrotoluene diisocyanate; 1,2-, 1,3-, and 1,4-phenylenediisocyanate; aromatic aliphatic isocyanate, such as 1,2-, 1,3-, and1,4-xylene diisocyanate; meta-tetramethylxylene diisocyanate (m-TMXDI);para-tetramethylxylene diisocyanate (p-TMXDI); trimerized isocyanurateof any polyisocyanate, such as isocyanurate of toluene diisocyanate,trimer of diphenylmethane diisocyanate, trimer of tetramethylxylenediisocyanate, isocyanurate of hexamethylene diisocyanate, isocyanurateof isophorone diisocyanate, and mixtures thereof; dimerized uredione ofany polyisocyanate, such as uretdione of toluene diisocyanate, uretdioneof hexamethylene diisocyanate, and mixtures thereof; modifiedpolyisocyanate derived from the above isocyanates and polyisocyanates;and mixtures thereof.

Examples of saturated diisocyanates that can be used with the presentinvention include, but are not limited to, ethylene diisocyanate;propylene-1,2-diisocyanate; tetramethylene diisocyanate;tetramethylene-1,4-diisocyanate; 1,6-hexamethylene-diisocyanate (HDI);octamethylene diisocyanate; decamethylene diisocyanate;2,2,4-trimethylhexamethylene diisocyanate; 2,4,4-trimethylhexamethylenediisocyanate; dodecane-1,12-diisocyanate; cyclobutane-1,3-diisocyanate;cyclohexane-1,2-diisocyanate; cyclohexane-1,3-diisocyanate;cyclohexane-1,4-diisocyanate; methyl-cyclohexylene diisocyanate (HTDI);2,4-methylcyclohexane diisocyanate; 2,6-methylcyclohexane diisocyanate;4,4′-dicyclohexyl diisocyanate; 2,4′-dicyclohexyl diisocyanate;1,3,5-cyclohexane triisocyanate; isocyanatomethylcyclohexane isocyanate;1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane;isocyanatoethylcyclohexane isocyanate; bis(isocyanatomethyl)-cyclohexanediisocyanate; 4,4′-bis(isocyanatomethyl) dicyclohexane;2,4′-bis(isocyanatomethyl) dicyclohexane; isophorone diisocyanate(IPDI); triisocyanate of HDI; triisocyanate of2,2,4-trimethyl-1,6-hexane diisocyanate (TMDI); 4,4′-dicyclohexylmethanediisocyanate (H₁₂MDI); 2,4-hexahydrotoluene diisocyanate;2,6-hexahydrotoluene diisocyanate; and mixtures thereof. Aromaticaliphatic isocyanates may also be used to form light stable materials.Examples of such isocyanates include 1,2-, 1,3-, and 1,4-xylenediisocyanate; meta-tetramethylxylene diisocyanate (m-TMXDI);para-tetramethylxylene diisocyanate (p-TMXDI); trimerized isocyanurateof any polyisocyanate, such as isocyanurate of toluene diisocyanate,trimer of diphenylmethane diisocyanate, trimer of tetramethylxylenediisocyanate, isocyanurate of hexamethylene diisocyanate, isocyanurateof isophorone diisocyanate, and mixtures thereof; dimerized uredione ofany polyisocyanate, such as uretdione of toluene diisocyanate, uretdioneof hexamethylene diisocyanate, and mixtures thereof; modifiedpolyisocyanate derived from the above isocyanates and polyisocyanates;and mixtures thereof. In addition, the aromatic aliphatic isocyanatesmay be mixed with any of the saturated isocyanates listed above for thepurposes of this invention.

The number of unreacted NCO groups in the polyurea prepolymer ofisocyanate and polyether amine may be varied to control such factors asthe speed of the reaction, the resultant hardness of the composition,and the like. For instance, the number of unreacted NCO groups in thepolyurea prepolymer of isocyanate and polyether amine may be less thanabout 14 percent. In one embodiment, the polyurea prepolymer has fromabout 5 percent to about 11 percent unreacted NCO groups, and even morepreferably has from about 6 to about 9.5 percent unreacted NCO groups.In one embodiment, the percentage of unreacted NCO groups is about 3percent to about 9 percent. Alternatively, the percentage of unreactedNCO groups in the polyurea prepolymer may be about 7.5 percent or less,and more preferably, about 7 percent or less. In another embodiment, theunreacted NCO content is from about 2.5 percent to about 7.5 percent,and more preferably from about 4 percent to about 6.5 percent.

When formed, polyurea prepolymers may contain about 10 percent to about20 percent by weight of the prepolymer of free isocyanate monomer. Thus,in one embodiment, the polyurea prepolymer may be stripped of the freeisocyanate monomer. For example, after stripping, the prepolymer maycontain about 1 percent or less free isocyanate monomer. In anotherembodiment, the prepolymer contains about 0.5 percent by weight or lessof free isocyanate monomer.

The polyether amine may be blended with additional polyols to formulatecopolymers that are reacted with excess isocyanate to form the polyureaprepolymer. In one embodiment, less than about 30 percent polyol byweight of the copolymer is blended with the saturated polyether amine.In another embodiment, less than about 20 percent polyol by weight ofthe copolymer, preferably less than about 15 percent by weight of thecopolymer, is blended with the polyether amine. The polyols listed abovewith respect to the polyurethane prepolymer, e.g., polyether polyols,polycaprolactone polyols, polyester polyols, polycarbonate polyols,hydrocarbon polyols, other polyols, and mixtures thereof, are alsosuitable for blending with the polyether amine. The molecular weight ofthese polymers may be from about 200 to about 4000, but also may be fromabout 1000 to about 3000, and more preferably are from about 1500 toabout 2500.

The polyurea composition can be formed by crosslinking the polyureaprepolymer with a single curing agent or a blend of curing agents. Thecuring agent of the invention is preferably an amine-terminated curingagent, more preferably a secondary diamine curing agent so that thecomposition contains only urea linkages. In one embodiment, theamine-terminated curing agent may have a molecular weight of about 64 orgreater. In another embodiment, the molecular weight of the amine-curingagent is about 2000 or less. As discussed above, certainamine-terminated curing agents may be modified with a compatibleamine-terminated freezing point depressing agent or mixture ofcompatible freezing point depressing agents.

Suitable amine-terminated curing agents include, but are not limited to,ethylene diamine; hexamethylene diamine; 1-methyl-2,6-cyclohexyldiamine; tetrahydroxypropylene ethylene diamine; 2,2,4- and2,4,4-trimethyl-1,6-hexanediamine;4,4′-bis-(sec-butylamino)-dicyclohexylmethane;1,4-bis-(sec-butylamino)-cyclohexane;1,2-bis-(sec-butylamino)-cyclohexane; derivatives of4,4′-bis-(sec-butylamino)-dicyclohexylmethane; 4,4′-dicyclohexylmethanediamine; 1,4-cyclohexane-bis-(methylamine);1,3-cyclohexane-bis-(methylamine); diethylene glycol di-(aminopropyl)ether; 2-methylpentamethylene-diamine; diaminocyclohexane; diethylenetriamine; triethylene tetramine; tetraethylene pentamine; propylenediamine; 1,3-diaminopropane; dimethylamino propylamine; diethylaminopropylamine; dipropylene triamine; imido-bis-propylamine;monoethanolamine, diethanolamine; triethanolamine; monoisopropanolamine,diisopropanolamine; isophoronediamine;4,4′-methylenebis-(2-chloroaniline);3,5;dimethylthio-2,4-toluenediamine;3,5-dimethylthio-2,6-toluenediamine; 3,5-diethylthio-2,4-toluenediamine;3,5;diethylthio-2,6-toluenediamine;4,4′-bis-(sec-butylamino)-diphenylmethane and derivatives thereof;1,4-bis-(sec-butylamino)-benzene; 1,2-bis-(sec-butylamino)-benzene;N,N′-dialkylamino-diphenylmethane; N,N,N′,N′-tetrakis (2-hydroxypropyl)ethylene diamine; trimethyleneglycol-di-p-aminobenzoate;polytetramethyleneoxide-di-p-aminobenzoate;4,4′-methylenebis-(3-chloro-2,6-diethyleneaniline);4,4′-methylenebis-(2,6-diethylaniline); meta-phenylenediamine;paraphenylenediamine; and mixtures thereof. In one embodiment, theamine-terminated curing agent is4,4′-bis-(sec-butylamino)-dicyclohexylmethane.

Suitable saturated amine-terminated curing agents include, but are notlimited to, ethylene diamine; hexamethylene diamine;1-methyl-2,6-cyclohexyl diamine; tetrahydroxypropylene ethylene diamine;2,2,4- and 2,4,4-trimethyl-1,6-hexanediamine;4,4′-bis-(sec-butylamino)-dicyclohexylmethane;1,4-bis-(sec-butylamino)-cyclohexane;1,2-bis-(sec-butylamino)-cyclohexane; derivatives of4,4′-bis-(sec-butylamino)-dicyclohexylmethane; 4,4′-dicyclohexylmethanediamine; 4,4′-methylenebis-(2,6-diethylaminocyclohexane;1,4-cyclohexane-bis-(methylamine); 1,3-cyclohexane-bis-(methylamine);diethylene glycol di-(aminopropyl)ether; 2-methylpentamethylene-diamine;diaminocyclohexane; diethylene triamine; triethylene tetramine;tetraethylene pentamine; propylene diamine; 1,3-diaminopropane;dimethylamino propylamine; diethylamino propylamine;imido-bis-propylamine; monoethanolamine, diethanolamine;triethanolamine; monoisopropanolamine, diisopropanolamine;isophoronediamine; triisopropanolamine; and mixtures thereof. Inaddition, any of the polyether amines listed above may be used as curingagents to react with the polyurea prepolymers.

Suitable catalysts include, but are not limited to bismuth catalyst,oleic acid, triethylenediamine (DABCO®-33LV), di-butyltin dilaurate(DABCO®-T12) and acetic acid. The most preferred catalyst is di-butyltindilaurate (DABCO®-T12). DABCO® materials are manufactured by AirProducts and Chemicals, Inc.

Thermoplastic materials may be blended with other thermoplasticmaterials, but thermosetting materials are difficult if not impossibleto blend homogeneously after the thermosetting materials are formed.Preferably, the saturated polyurethane comprises from about 1% to about100%, more preferably from about 10% to about 75% of the covercomposition and/or the intermediate layer composition. About 90% toabout 10%, more preferably from about 90% to about 25% of the coverand/or the intermediate layer composition is comprised of one or moreother polymers and/or other materials as described below. Such polymersinclude, but are not limited to polyurethane/polyurea ionomers,polyurethanes or polyureas, epoxy resins, polyethylenes, polyamides andpolyesters, polycarbonates and polyacrylin. Unless otherwise statedherein, all percentages are given in percent by weight of the totalcomposition of the golf ball layer in question.

Polyurethane prepolymers are produced by combining at least one polyol,such as a polyether, polycaprolactone, polycarbonate or a polyester, andat least one isocyanate. Thermosetting polyurethanes are obtained bycuring at least one polyurethane prepolymer with a curing agent selectedfrom a polyamine, triol or tetraol. Thermoplastic polyurethanes areobtained by curing at least one polyurethane prepolymer with a diolcuring agent. The choice of the curatives is critical because someurethane elastomers that are cured with a diol and/or blends of diols donot produce urethane elastomers with the impact resistance required in agolf ball cover. Blending the polyamine curatives with diol curedurethane elastomeric formulations leads to the production of thermoseturethanes with improved impact and cut resistance.

Thermoplastic polyurethanes may be blended with suitable materials toproduce a thermoplastic end product. Examples of such additionalmaterials may include ionomers such as the SURLYN®, ESCOR® and IOTEK®copolymers described above.

Other suitable materials which may be combined with the saturatedpolyurethanes in forming the cover and/or intermediate layer(s) of thegolf balls of the invention include ionic or non-ionic polyurethanes andpolyureas, epoxy resins, polyethylenes, polyamides and polyesters. Forexample, the cover and/or intermediate layer may be formed from a blendof at least one saturated polyurethane and thermoplastic or thermosetionic and non-ionic urethanes and polyurethanes, cationic urethaneionomers and urethane epoxies, ionic and non-ionic polyureas and blendsthereof. Examples of suitable urethane ionomers are disclosed in U.S.Pat. No. 5,692,974 entitled “Golf Ball Covers”, the disclosure of whichis hereby incorporated by reference in its entirety. Other examples ofsuitable polyurethanes are described in U.S. Pat. No. 5,334,673.Examples of appropriate polyureas are discussed in U.S. Pat. No.5,484,870 and examples of suitable polyurethanes cured with epoxy groupcontaining curing agents are disclosed in U.S. Pat. No. 5,908,358, thedisclosures of which are hereby incorporated herein by reference intheir entirety.

A variety of conventional components can be added to the covercompositions of the present invention. These include, but are notlimited to, white pigment such as TiO₂, ZnO, optical brighteners,surfactants, processing aids, foaming agents, density-controllingfillers, UV stabilizers and light stabilizers. Saturated polyurethanesare resistant to discoloration. However, they are not immune todeterioration in their mechanical properties upon weathering. Additionof UV absorbers and light stabilizers therefore helps to maintain thetensile strength and elongation of the saturated polyurethaneelastomers. Suitable UV absorbers and light stabilizers include TINUVIN®328, TINUVIN® 213, TINUVIN® 765, TINUVIN® 770 and TINUVIN® 622. Thepreferred UV absorber is TINUVIN® 328, and the preferred lightstabilizer is TINUVIN® 765. TINUVIN® products are available fromCiba-Geigy. Dyes, as well as optical brighteners and fluorescentpigments may also be included in the golf ball covers produced withpolymers formed according to the present invention. Such additionalingredients may be added in any amounts that will achieve their desiredpurpose.

Any method known to one of ordinary skill in the art may be used topolyurethanes of the present invention. One commonly employed method,known in the art as a one-shot method, involves concurrent mixing of thepolyisocyanate, polyol, and curing agent. This method results in amixture that is inhomogenous (more random) and affords the manufacturerless control over the molecular structure of the resultant composition.A preferred method of mixing is known as a prepolymer method. In thismethod, the polyisocyanate and the polyol are mixed separately prior toaddition of the curing agent. This method affords a more homogeneousmixture resulting in a more consistent polymer composition. Othermethods suitable for forming the layers of the present invention includereaction injection molding (“RIM”), liquid injection molding (“LIM”),and pre-reacting the components to form an injection moldablethermoplastic polyurethane and then injection molding, all of which areknown to one of ordinary skill in the art.

Additional components which can be added to the polyurethane compositioninclude UV stabilizers and other dyes, as well as optical brightenersand fluorescent pigments and dyes. Such additional ingredients may beadded in any amounts that will achieve their desired purpose. It hasbeen found by the present invention that the use of a castable, reactivematerial, which is applied in a fluid form, makes it possible to obtainvery thin outer cover layers on golf balls. Specifically, it has beenfound that castable, reactive liquids, which react to form a urethaneelastomer material, provide desirable very thin outer cover layers.

The castable, reactive liquid employed to form the urethane elastomermaterial can be applied over the core using a variety of applicationtechniques such as spraying, dipping, spin coating, or flow coatingmethods which are well known in the art. An example of a suitablecoating technique is that which is disclosed in U.S. Pat. No. 5,733,428,the disclosure of which is hereby incorporated by reference in itsentirety.

The outer cover is preferably formed around the inner cover by mixingand introducing the material in the mold halves. It is important thatthe viscosity be measured over time, so that the subsequent steps offilling each mold half, introducing the core into one half and closingthe mold can be properly timed for accomplishing centering of the corecover halves fusion and achieving overall uniformity. Suitable viscosityrange of the curing urethane mix for introducing cores into the moldhalves is determined to be approximately between about 2,000 cP andabout 30,000 cP, with the preferred range of about 8,000 cP to about15,000 cP.

To start the cover formation, mixing of the prepolymer and curative isaccomplished in motorized mixer including mixing head by feeding throughlines metered amounts of curative and prepolymer. Top preheated moldhalves are filled and placed in fixture units using centering pinsmoving into holes in each mold. At a later time, a bottom mold half or aseries of bottom mold halves have similar mixture amounts introducedinto the cavity. After the reacting materials have resided in top moldhalves for about 40 to about 80 seconds, a core is lowered at acontrolled speed into the gelling reacting mixture.

A ball cup holds the ball core through reduced pressure (or partialvacuum). Upon location of the coated core in the halves of the moldafter gelling for about 40 to about 80 seconds, the vacuum is releasedallowing core to be released. The mold halves, with core and solidifiedcover half thereon, are removed from the centering fixture unit,inverted and mated with other mold halves which, at an appropriate timeearlier, have had a selected quantity of reacting polyurethaneprepolymer and curing agent introduced therein to commence gelling.

Similarly, U.S. Pat. No. 5,006,297 to Brown et al. and U.S. Pat. No.5,334,673 to Wu both also disclose suitable molding techniques which maybe utilized to apply the castable reactive liquids employed in thepresent invention. Further, U.S. Pat. Nos. 6,180,040 and 6,180,722disclose methods of preparing dual core golf balls. The disclosures ofthese patents are hereby incorporated by reference in their entirety.However, the method of the invention is not limited to the use of thesetechniques.

Depending on the desired properties, balls prepared according to theinvention can exhibit substantially the same or higher resilience, orcoefficient of restitution (“COR”), with a decrease in compression ormodulus, compared to balls of conventional construction. Additionally,balls prepared according to the invention can also exhibit substantiallyhigher resilience, or COR, without an increase in compression, comparedto balls of conventional construction. Another measure of thisresilience is the “loss tangent,” or tan 6, which is obtained whenmeasuring the dynamic stiffness of an object. Loss tangent andterminology relating to such dynamic properties is typically describedaccording to ASTM D4092-90. Thus, a lower loss tangent indicates ahigher resiliency, thereby indicating a higher rebound capacity. Lowloss tangent indicates that most of the energy imparted to a golf ballfrom the club is converted to dynamic energy, i.e., launch velocity andresulting longer distance. The rigidity or compressive stiffness of agolf ball may be measured, for example, by the dynamic stiffness. Ahigher dynamic stiffness indicates a higher compressive stiffness. Toproduce golf balls having a desirable compressive stiffness, the dynamicstiffness of the crosslinked reaction product material should be lessthan about 50,000 N/m at −50° C. Preferably, the dynamic stiffnessshould be between about 10,000 and 40,000 N/m at −50° C., morepreferably, the dynamic stiffness should be between about 20,000 and30,000 N/m at −50° C.

The molding process and composition of golf ball portions typicallyresults in a gradient of material properties. Methods employed in theprior art generally exploit hardness to quantify these gradients.Hardness is a qualitative measure of static modulus and does notrepresent the modulus of the material at the deformation ratesassociated with golf ball use, i.e., impact by a club. As is well knownto one skilled in the art of polymer science, the time-temperaturesuperposition principle may be used to emulate alternative deformationrates. For golf ball portions including polybutadiene, a 1-Hzoscillation at temperatures between 0° C. and −50° C. are believed to bequalitatively equivalent to golf ball impact rates. Therefore,measurement of loss tangent and dynamic stiffness at 0° C. to −50° C.may be used to accurately anticipate golf ball performance, preferablyat temperatures between about −20° C. and −50° C.

U.S. application Ser. No. 10/230,015, now U.S. Publication No.2003/0114565, and U.S. application Ser. No. 10/108,793, now U.S.Publication No. 2003/0050373, which are incorporated by reference hereinin their entirety, discuss soft, high resilient ionomers, which arepreferably from neutralizing the acid copolymer(s) of at least one E/X/Ycopolymer, where E is ethylene, X is the α,β-ethylenically unsaturatedcarboxylic acid, and Y is a softening co-monomer. X is preferablypresent in 2-30 (preferably 4-20, most preferably 5-15) wt. % of thepolymer, and Y is preferably present in 17-40 (preferably 20-40, andmore preferably 24-35) wt. % of the polymer. Preferably, the melt index(MI) of the base resin is at least 20, or at least 40, more preferably,at least 75 and most preferably at least 150. Particular soft, resilientionomers included in this invention are partially neutralizedethylene/(meth) acrylic acid/butyl (meth) acrylate copolymers having anMI and level of neutralization that results in a melt processiblepolymer that has useful physical properties. The copolymers are at leastpartially neutralized. Preferably at least 40, or, more preferably atleast 55, even more preferably about 70, and most preferably about 80 ofthe acid moiety of the acid copolymer is neutralized by one or morealkali metal, transition metal, or alkaline earth metal cations. Cationsuseful in making the ionomers of this invention comprise lithium,sodium, potassium, magnesium, calcium, barium, or zinc, or a combinationof such cations.

The invention also relates to a “modified” soft, resilient thermoplasticionomer that comprises a melt blend of (a) the acid copolymers or themelt processible ionomers made therefrom as described above and (b) oneor more organic acid(s) or salt(s) thereof, wherein greater than 80%,preferably greater than 90% of all the acid of (a) and of (b) isneutralized. Preferably, 100% of all the acid of (a) and (b) isneutralized by a cation source. Preferably, an amount of cation sourcein excess of the amount required to neutralize 100% of the acid in (a)and (b) is used to neutralize the acid in (a) and (b). Blends with fattyacids or fatty acid salts are preferred.

The organic acids or salts thereof are added in an amount sufficient toenhance the resilience of the copolymer. Preferably, the organic acidsor salts thereof are added in an amount sufficient to substantiallyremove remaining ethylene crystallinity of the copolymer.

Preferably, the organic acids or salts are added in an amount of atleast about 5% (weight basis) of the total amount of copolymer andorganic acid(s). More preferably, the organic acids or salts thereof areadded in an amount of at least about 15%, even more preferably at leastabout 20%. Preferably, the organic acid(s) are added in an amount up toabout 50% (weight basis) based on the total amount of copolymer andorganic acid. More preferably, the organic acids or salts thereof areadded in an amount of up to about 40%, more preferably, up to about 35%.The non-volatile, non-migratory organic acids preferably are one or morealiphatic, mono-functional organic acids or salts thereof as describedbelow, particularly one or more aliphatic, mono-functional, saturated orunsaturated organic acids having less than 36 carbon atoms or salts ofthe organic acids, preferably stearic acid or oleic acid. Fatty acids orfatty acid salts are most preferred.

Processes for fatty acid (salt) modifications are known in the art.Particularly, the modified highly-neutralized soft, resilient acidcopolymer ionomers of this invention can be produced by:

(a) melt-blending (1) ethylene, α,β-ethylenically unsaturated C₃₋₈carboxylic acid copolymer(s) or melt-processible ionomer(s) thereof thathave their crystallinity disrupted by addition of a softening monomer orother means with (2) sufficient non-volatile, non-migratory organicacids to substantially enhance the resilience and to disrupt (preferablyremove) the remaining ethylene crystallinity, and then concurrently orsubsequently

(b) adding a sufficient amount of a cation source to increase the levelof neutralization of all the acid moieties (including those in the acidcopolymer and in the organic acid if the non-volatile, non-migratoryorganic acid is an organic acid) to the desired level.

The weight ratio of X to Y in the composition is at least about 1:20.Preferably, the weight ratio of X to Y is at least about 1:15, morepreferably, at least about 1:10. Furthermore, the weight ratio of X to Yis up to about 1:1.67, more preferably up to about 1:2. Most preferably,the weight ratio of X to Y in the composition is up to about 1:2.2.

The acid copolymers used in the present invention to make the ionomersare preferably ‘direct’ acid copolymers (containing high levels ofsoftening monomers). As noted above, the copolymers are at leastpartially neutralized, preferably at least about 40% of X in thecomposition is neutralized. More preferably, at least about 55% of X isneutralized. Even more preferably, at least about 70, and mostpreferably, at least about 80% of X is neutralized. In the event thatthe copolymer is highly neutralized (e.g., to at least 45%, preferably50%, 55%, 70%, or 80%, of acid moiety), the MI of the acid copolymershould be sufficiently high so that the resulting neutralized resin hasa measurable MI in accord with ASTM D-1238, condition E, at 190° C.,using a 2160 gram weight. Preferably this resulting MI will be at least0.1, preferably at least 0.5, and more preferably 1.0 or greater.Preferably, for highly neutralized acid copolymer, the MI of the acidcopolymer base resin is at least 20, or at least 40, at least 75, andmore preferably at least 150.

The acid copolymers preferably comprise alpha olefin, particularlyethylene, C₃₋₈ α,β-ethylenically unsaturated carboxylic acid,particularly acrylic and methacrylic acid, and softening monomers,selected from alkyl acrylate, and alkyl methacrylate, wherein the alkylgroups have from 1-8 carbon atoms, copolymers. By “softening,” it ismeant that the crystallinity is disrupted (the polymer is made lesscrystalline). While the alpha olefin can be a C₂-C₄ alpha olefin,ethylene is most preferred for use in the present invention.Accordingly, it is described and illustrated herein in terms of ethyleneas the alpha olefin.

The acid copolymers, when the alpha olefin is ethylene, can be describedas E/X/Y copolymers where E is ethylene, X is the α,β-ethylenicallyunsaturated carboxylic acid, and Y is a softening comonomer; X ispreferably present in 2-30 (preferably 4-20, most preferably 5-15) wt. %of the polymer, and Y is preferably present in 17-40 (preferably 20-40,most preferably 24-35) wt. % of the polymer.

The ethylene-acid copolymers with high levels of acid (X) are difficultto prepare in continuous polymerizers because of monomer-polymer phaseseparation. This difficulty can be avoided however by use of “co-solventtechnology” as described in U.S. Pat. No. 5,028,674, or by employingsomewhat higher pressures than those which copolymers with lower acidcan be prepared.

Specific acid-copolymers include ethylene/(meth) acrylic acid/n-butyl(meth) acrylate, ethylene/(meth) acrylic acid/iso-butyl (meth) acrylate,ethylene/(meth) acrylic acid/methyl (meth) acrylate, and ethylene/(meth)acrylic acid/ethyl (meth) acrylate terpolymers.

The organic acids employed are aliphatic, mono-functional (saturated,unsaturated, or multi-unsaturated) organic acids, particularly thosehaving fewer than 36 carbon atoms. Also salts of these organic acids maybe employed. Fatty acids or fatty acid salts are preferred. The saltsmay be any of a wide variety, particularly including the barium,lithium, sodium, zinc, bismuth, potassium, strontium, magnesium orcalcium salts of the organic acids. Particular organic acids useful inthe present invention include caproic acid, caprylic acid, capric acid,lauric acid, stearic acid, behenic acid, erucic acid, oleic acid, andlinoleic acid.

The optional filler component is chosen to impart additional density toblends of the previously described components, the selection beingdependent upon the different parts (e.g., cover, mantle, core, center,intermediate layers in a multilayered core or ball) and the type of golfball desired (e.g., one-piece, two-piece, three-piece or multiple-pieceball), as will be more fully detailed below.

Generally, the filler will be inorganic having a density greater thanabout 4 g/cm³, preferably greater than 5 g/cm³, and will be present inamounts between 0 to about 60 wt. % based on the total weight of thecomposition. Examples of useful fillers include zinc oxide, bariumsulfate, lead silicate and tungsten carbide, as well as the otherwell-known fillers used in golf balls. It is preferred that the fillermaterials be non-reactive or almost non-reactive and not stiffen orraise the compression nor reduce the coefficient of restitutionsignificantly.

Additional optional additives useful in the practice of the subjectinvention include acid copolymer wax (e.g., Allied wax AC 143 believedto be an ethylene/16-18% acrylic acid copolymer with a number averagemolecular weight of 2,040), which assist in preventing reaction betweenthe filler materials (e.g., ZnO) and the acid moiety in the ethylenecopolymer. Other optional additives include TiO₂, which is used as awhitening agent; optical brighteners; surfactants; processing aids; etc.

Ionomers may be blended with conventional ionomeric copolymers (di-,ter-, etc.), using well-known techniques, to manipulate productproperties as desired. The blends would still exhibit lower hardness andhigher resilience when compared with blends based on conventionalionomers.

Also, ionomers can be blended with non-ionic thermoplastic resins tomanipulate product properties. The non-ionic thermoplastic resins would,by way of non-limiting illustrative examples, include thermoplasticelastomers, such as polyurethane, poly-ether-ester, poly-amide-ether,polyether-urea, PEBAX® (a family of block copolymers based onpolyether-block-amide, commercially supplied by Atochem),styrene-butadiene-styrene (SBS) block copolymers,styrene(ethylene-butylene)-styrene block copolymers, etc., poly amide(oligomeric and polymeric), polyesters, polyolefins including PE, PP,E/P copolymers, etc., ethylene copolymers with various comonomers, suchas vinyl acetate, (meth)acrylates, (meth)acrylic acid,epoxy-functionalized monomer, CO, etc., functionalized polymers withmaleic anhydride grafting, epoxidization etc., elastomers, such as EPDM,metallocene catalyzed PE and copolymer, ground up powders of thethermoset elastomers, etc. Such thermoplastic blends comprise about 1%to about 99% by weight of a first thermoplastic and about 99% to about1% by weight of a second thermoplastic.

Additionally, the compositions of U.S. application Ser. No. 10/269,341,now U.S. Publication No. 2003/0130434, and U.S. Pat. No. 6,653,382, bothof which are incorporated herein in their entirety, discuss compositionshaving high COR when formed into solid spheres.

The thermoplastic composition of this invention comprises a polymerwhich, when formed into a sphere that is 1.50 to 1.54 inches indiameter, has a coefficient of restitution (COR) when measured by firingthe sphere at an initial velocity of 125 feet/second against a steelplate positioned 3 feet from the point where initial velocity andrebound velocity are determined and by dividing the rebound velocityfrom the plate by the initial velocity and an Atti compression of nomore than 100.

The thermoplastic composition of this invention preferably comprises (a)aliphatic, mono-functional organic acid(s) having fewer than 36 carbonatoms; and (b) ethylene, C₃ to C₈ α,β-ethylenically unsaturatedcarboxylic acid copolymer(s) and ionomer(s) thereof, wherein greaterthan 90%, preferably near 100%, and more preferably 100% of all the acidof (a) and (b) are neutralized.

The thermoplastic composition preferably comprises melt-processible,highly-neutralized (greater than 90%, preferably near 100%, and morepreferably 100%) polymer of (1) ethylene, C₃ to C₈ α,β-ethylenicallyunsaturated carboxylic acid copolymers that have their crystallinitydisrupted by addition of a softening monomer or other means such as highacid levels, and (2) non-volatile, non-migratory agents such as organicacids (or salts) selected for their ability to substantially or totallysuppress any remaining ethylene crystallinity. Agents other than organicacids (or salts) may be used.

It has been found that, by modifying an acid copolymer or ionomer with asufficient amount of specific organic acids (or salts thereof); it ispossible to highly neutralize the acid copolymer without losingprocessibility or properties such as elongation and toughness. Theorganic acids employed in the present invention are aliphatic,mono-functional, saturated or unsaturated organic acids, particularlythose having fewer than 36 carbon atoms, and particularly those that arenon-volatile and non-migratory and exhibit ionic array plasticizing andethylene crystallinity suppression properties.

With the addition of sufficient organic acid, greater than 90%, nearly100%, and preferably 100% of the acid moieties in the acid copolymerfrom which the ionomer is made can be neutralized without losing theprocessibility and properties of elongation and toughness.

The melt-processible, highly-neutralized acid copolymer ionomer can beproduced by the following:

(a) melt-blending (1) ethylene α,β-ethylenically unsaturated C₃₋₈carboxylic acid copolymer(s) or melt-processible ionomer(s) thereof(ionomers that are not neutralized to the level that they have becomeintractable, that is not melt-processible) with (1) one or morealiphatic, mono-functional, saturated or unsaturated organic acidshaving fewer than 36 carbon atoms or salts of the organic acids, andthen concurrently or subsequently

(b) adding a sufficient amount of a cation source to increase the levelof neutralization all the acid moieties (including those in the acidcopolymer and in the organic acid) to greater than 90%, preferably near100%, more preferably to 100%.

Preferably, highly-neutralized thermoplastics of the invention can bemade by:

(a) melt-blending (1) ethylene, α,β-ethylenically unsaturated C₃₋₈carboxylic acid copolymer(s) or melt-processible ionomer(s) thereof thathave their crystallinity disrupted by addition of a softening monomer orother means with (2) sufficient non-volatile, non-migratory agents tosubstantially remove the remaining ethylene crystallinity, and thenconcurrently or subsequently

(b) adding a sufficient amount of a cation source to increase the levelof neutralization all the acid moieties (including those in the acidcopolymer and in the organic acid if the non-volatile, non-migratoryagent is an organic acid) to greater than 90%, preferably near 100%,more preferably to 100%.

The acid copolymers used in the present invention to make the ionomersare preferably ‘direct’ acid copolymers. They are preferably alphaolefin, particularly ethylene, C₃₋₈ α,β-ethylenically unsaturatedcarboxylic acid, particularly acrylic and methacrylic acid, copolymers.They may optionally contain a third softening monomer. By “softening,”it is meant that the crystallinity is disrupted (the polymer is madeless crystalline). Suitable “softening” comonomers are monomers selectedfrom alkyl acrylate, and alkyl methacrylate, wherein the alkyl groupshave from 1-8 carbon atoms.

The acid copolymers, when the alpha olefin is ethylene, can be describedas E/Y/Y copolymers where E is ethylene, X is the α,β-ethylenicallyunsaturated carboxylic acid, and Y is a softening comonomer. X ispreferably present in 3-30 (preferably 4-25, most preferably 5-20) wt. %of the polymer, and Y is preferably present in 0-30 (alternatively 3-25or 10-23) wt. % of the polymer.

Spheres were prepared using fully neutralized ionomers A and B.

TABLE I Resin Acid Type Cation (% M.I. Sample Type (%) (%) neut*) (g/10mm) 1A A(60) Oleic (40) Mg (100) 1.0 2B A(60) Oleic (40) Mg (105)* 0.93C B(60) Oleic (40) Mg (100) 0.9 4D B(60) Oleic (40) Mg (105)* 0.9 5EB(60) Stearic Mg (100) 0.85 (40) A - 76.9% ethylene, 14.8% normal butylacrylate, 8.3% acrylic acid B - 75% ethylene, 14.9% normal butylacrylate, 10.1% acrylic acid *indicates that cation was sufficient toneutralize 105% of all the acid in the resin and the organic acid.

These compositions were molded into 1.53-inch spheres for which data ispresented in the following table.

TABLE II Sample Atti Compression COR @ 125 ft/s 1A 75 0.826 2B 75 0.8263C 78 0.837 4D 76 0.837 5E 97 0.807

Further testing of commercially available highly neutralized polymersHNP1 and HNP2 had the following properties.

TABLE III Material Properties HNP1 HNP2 Specific Gravity (g/cm³) 0.9660.974 Melt Flow, 190° C., 10-kg load 0.65 1.0 Shore D Flex Bar (40 hr)47.0 46.0 Shore D Flex Bar (2 week) 51.0 48.0 Flex Modulus, psi (40 hr)25,800 16,100 Flex Modulus, psi (2 week) 39,900 21,000 DSC Melting Point(° C.) 61.0 61/101 Moisture (ppm) 1500 4500 Weight % Mg 2.65 2.96

TABLE IV Solid Sphere Data HNP1a/HNP2a Material HNP1 HNP2 HNP2a HNP1a(50:50 blend) Spec. Grav. 0.954 0.959 1.153 1.146 1.148 (g/cm³) FillerNone None Tungsten Tungsten Tungsten Compression 107 83 86 62 72 COR0.827 0.853 0.844 0.806 0.822 Shore D 51 47 49 42 45 Shore C 79 72 75

These materials are exemplary examples of the preferred center and/orcore layer compositions of the present invention. They may also be usedas a cover layer herein.

The golf ball components of the present invention, in particular thecore (center and/or outer core layers) may be formed from a co-polymerof ethylene and an α,β-unsaturated carboxylic acid. In anotherembodiment, they may be formed from a terpolymer of ethylene, anα,β-unsaturated carboxylic acid, and an n-alkyl acrylate. Preferably,the α,β-unsaturated carboxylic acid is acrylic acid or methacrylic acid.In a preferred embodiment, the n-alkyl acrylate is n-butyl acrylate.Further, in a preferred form, the co- or ter-polymer comprises a levelof fatty acid salt greater than 5 phr of the base resin. The preferredfatty acid salt is magnesium oleate or magnesium stearate.

It is highly preferred that the carboxylic acid in the intermediatelayer is 100% neutralized with metal ions. The metal ions used toneutralize the carboxylic acid may be any metal ion known in the art.Preferably, the metal ions comprise magnesium ions. If the material usedin the intermediate layer is not 100% neutralized, the resultantresilience properties such as COR and initial velocity may not besufficient to produce the improved initial velocity and distanceproperties of the present invention.

The golf ball components can comprise various levels of the threecomponents of the co- or terpolymer as follows: from about 60 to about90% ethylene, from about 8 to about 20% by weight of the α,β-unsaturatedcarboxylic acid, and from 0% to about 25% of the n-alkyl acrylate. Theco- or terpolymer may also contain an amount of a fatty acid salt. Thefatty acid salt preferably comprises magnesium oleate. These materialsare commercially available from DuPont, under the tradename DuPont HPF®.

In one embodiment, the core and/or core layers (or other intermediatelayers) comprises a copolymer of about 81% by weight ethylene and about19% by weight acrylic acid, wherein 100% of the carboxylic acid groupsare neutralized with magnesium ions. The copolymer also contains atleast 5 phr of magnesium oleate. Material suitable for use as this layeris available from DuPont under the tradename DuPont HPF SEP 1313-4®.

In a second preferred embodiment, the core and/or core layers (or otherintermediate layers) comprise a copolymer of about 85% by weightethylene and about 15% by weight acrylic acid, wherein 100% of the acidgroups are neutralized with magnesium ions. The copolymer also containsat least 5 phr of magnesium oleate. Material suitable for use as thislayer is available from DuPont under the tradename DuPont HPF SEP1313-3®.

In a third preferred embodiment, the core and/or core layers (or otherintermediate layers) comprise a copolymer of about 88% by weightethylene and about 12% by weight acrylic acid, wherein 100% of the acidgroups are neutralized with magnesium ions. The copolymer also containsat least 5 phr of magnesium oleate. Material suitable for use as thislayer is available from DuPont under the tradename DuPont HPF AD1027®.

In a further preferred embodiment, the core and/or core layers (or otherintermediate layers) are adjusted to a target specific gravity to enablethe ball to be balanced. For a 1.68-inch diameter golf ball having aball weight of about 1.61 oz, the target specific gravity is about1.125. It will be appreciated by one of ordinary skill in the art thatthe target specific gravity will vary based upon the size and weight ofthe golf ball. The specific gravity is adjusted to the desired targetthrough the use of inorganic fillers. Preferred fillers used forcompounding the inner layer to the desired specific gravity include, butare not limited to, tungsten, zinc oxide, barium sulfate and titaniumdioxide. Other suitable fillers, in particular nano or hybrid materials,include those described in U.S. Pat. No. 6,793,592 and U.S. applicationSer. No. 10/037,987, which are incorporated herein, in their entirety,by reference thereto.

Some preferred golf ball layers formed from the above compositions weremolded onto a golf ball center using DuPont HPF RX-85®, Dupont HPF SEP1313-3®, or DuPont HPF SEP 1313-4®. 1) DuPont HPF RX-85®, a copolymer ofabout 88% ethylene and about 12% acrylic acid, wherein 100% of the acidgroups are neutralized with magnesium ions. Further, the copolymercontains a fixed amount of magnesium oleate. This material wascompounded to a specific gravity of about 1.125 using tungsten. TheShore D hardness of this material (as measured on the curved surface ofthe inner cover layer) was about 58 to about 60. 2) DuPont HPF SEP1313-3®, a copolymer of about 85% ethylene and about 15% acrylic acid,wherein 100% of the acid groups are neutralized with magnesium ions.Further, the copolymer contains a fixed amount of magnesium oleate. Thismaterial was compounded to a specific gravity of about 1.125 usingtungsten. The Shore D hardness of this material (as measured on thecurved surface of the inner cover layer) was about 58-60. 3) DuPont HPFSEP 1313-4®, a copolymer of about 81% ethylene and about 19% acrylicacid, wherein 100% of the acid groups are neutralized with magnesiumions. Further, the copolymer contains a fixed amount of magnesiumoleate. This material was compounded to a specific gravity of about1.125 using tungsten. The Shore D hardness of this material (as measuredon the curved surface of the inner cover layer) was about 58-60.

The centers/cores/layers can also comprise various levels of the threecomponents of the terpolymer as follows: from about 60% to 80% ethylene;from about 8% to 20% by weight of the α,β-unsaturated carboxylic acid;and from about 0% to 25% of the n-alkyl acrylate, preferably 5% to 25%.The terpolymer will also contain an amount of a fatty acid salt,preferably magnesium oleate. These materials are commercially availableunder the trade name DuPont® HPF™. In a preferred embodiment, aterpolymer suitable for the invention will comprise from about 75% to80% by weight ethylene, from about 8% to 12% by weight of acrylic acid,and from about 8% to 17% by weight of n-butyl acrylate, wherein all ofthe carboxylic acid is neutralized with magnesium ions, and comprises atleast 5 phr of magnesium oleate.

In another preferred embodiment, the cover layer will comprise aterpolymer of about 70% to 75% by weight ethylene, about 10.5% by weightacrylic acid, and about 15.5% to 16.5% by weight n-butyl acrylate. Theacrylic acid groups are 100% neutralized with magnesium ions. Theterpolymer will also contain an amount of magnesium oleate. Materialssuitable for use as this layer are sold under the trade name DuPont®HPF™ AD 1027.

In yet another preferred embodiment, the centers/cores/layers comprise acopolymer comprising about 88% by weight of ethylene and about 12% byweight acrylic acid, with 100% of the acrylic acid neutralized bymagnesium ions. The centers/cores/layers may also contain magnesiumoleate. Material suitable for this embodiment was produced by DuPont asexperimental product number SEP 1264-3. Preferably thecenters/cores/layers are adjusted to a target specific gravity of 1.125using inert fillers to adjust the density with minimal effect on theperformance properties of the cover layer. Preferred fillers used forcompounding the centers/cores/layers to the desired specific gravityinclude but are not limited to tungsten, zinc oxide, barium sulfate, andtitanium dioxide.

A first set of intermediate layers were molded onto cores using DuPont®HPF™ AD1027, which is a terpolymer of about 73% to 74% ethylene, about10.5% acrylic acid, and about 15.5% to 16.5% n-butyl acrylate, wherein100% of the acid groups are neutralized with magnesium ions. Further,the terpolymer contains a fixed amount of greater than 5 phr magnesiumoleate. This material is compounded to a specific gravity of about 1.125using barium sulfate and titanium dioxide. The Shore D hardness of thismaterial (as measured on the curved surface of the inner cover layer) isabout 58-60.

A second set of layers were molded onto each of the experimental coresusing DuPont experimental HPF™ SEP 1264-3, which is a copolymer of about88% ethylene and about 12% acrylic acid, wherein 100% of the acid groupsare neutralized with magnesium ions. Further, the copolymer contains afixed amount of at least 5 phr magnesium oleate. This material iscompounded to a specific gravity of about 1.125 using zinc oxide. TheShore D hardness of this material (as measured on the curved surface ofthe inner cover layer) is about 61-64.

A first set of covers were molded onto each of the core/layer componentsusing DuPont HPF™ 1000, which is a terpolymer of about 75% to 76%ethylene, about 8.5% acrylic acid, and about 15.5% to 16.5% n-butylacrylate, wherein 100% of the acid groups are neutralized with magnesiumions. Further, the terpolymer contains a fixed amount of at least 5 phrof magnesium stearate. This material is compounded to a target specificgravity of about 1.125 using barium sulfate and titanium dioxide. TheShore D hardness of this material (as measured on the curved surface ofthe molded golf ball) is about 60-62.

In one embodiment, the formation of a golf ball starts with forming theinner core. The inner core, outer core, and the cover are formed bycompression molding, by injection molding, or by casting. These methodsof forming cores and covers of this type are well known in the art. Thematerials used for the inner and outer core, as well as the cover, areselected so that the desired playing characteristics of the ball areachieved. The inner and outer core materials have substantiallydifferent material properties so that there is a predeterminedrelationship between the inner and outer core materials, to achieve thedesired playing characteristics of the ball.

In one embodiment, the inner core is formed of a first material having afirst Shore D hardness, a first elastic modulus, a first specificgravity, and a first Bashore resilience. The outer core is formed of asecond material having a second Shore D hardness, a second elasticmodulus, a second specific gravity, and a second Bashore resilience.Preferably, the material property of the first material equals at leastone selected from the group consisting of the first Shore D hardnessdiffering from the second Shore D hardness by at least 10 points, thefirst elastic modulus differing from the second elastic modulus by atleast 10%, the first specific gravity differing from the second specificgravity by at least 0.1, or a first Bashore resilience differing fromthe second Bashore resilience by at least 10%. It is more preferred thatthe first material have all of these material property relationships.

Moreover, it is preferred that the first material has the first Shore Dhardness between about 30 and about 80, the first elastic modulusbetween about 5,000 psi and about 100,000 psi, the first specificgravity between about 0.8 and about 1.6, and the first Bashoreresilience greater than 30%.

In another embodiment, the first Shore D hardness is less than thesecond Shore D hardness, the first elastic modulus is less than thesecond elastic modulus, the first specific gravity is less than thesecond specific gravity, and the first Bashore resilience is less thanthe second Bashore resilience. In another embodiment, the first materialproperties are greater than the second material properties. Therelationship between the first and second material properties depends onthe desired playability characteristics.

Suitable inner and outer core materials include HNP's neutralized withorganic fatty acids and salts thereof, metal cations, or a combinationof both, thermosets, such as rubber, polybutadiene, polyisoprene;thermoplastics, such as ionomer resins, polyamides or polyesters; orthermoplastic elastomers. Suitable thermoplastic elastomers includePEBAX®, HYTREL®, thermoplastic urethane, and KRATON®, which arecommercially available from Elf-Atochem, DuPont, BF Goodrich, and Shell,respectively. The inner and outer core materials can also be formed froma castable material. Suitable castable materials include, but are notlimited to, urethane, urea, epoxy, diols, or curatives.

The cover is selected from conventional materials used as golf ballcovers based on the desired performance characteristics. The cover maybe comprised of one or more layers. Cover materials such as ionomerresins, blends of ionomer resins, thermoplastic or thermoset urethanes,and balata, can be used as known in the art and discussed above. Inother embodiments, additional layers may be added to those mentionedabove or the existing layers may be formed by multiple materials.

When the core is formed with a fluid-filled center, the center is formedfirst then the inner core is molded around the center. Conventionalmolding techniques can be used for this operation. Then the outer coreand cover are formed thereon, as discussed above. The fluid within theinner core can be a wide variety of materials including air, watersolutions, liquids, gels, foams, hot-melts, other fluid materials andcombinations thereof. The fluid is varied to modify the performanceparameters of the ball, such as the moment of inertia or the spin decayrate. Examples of suitable liquids include either solutions such as saltin water, corn syrup, salt in water and corn syrup, glycol and water oroils. The liquid can further include pastes, colloidal suspensions, suchas clay, barytes, carbon black in water or other liquid, or salt inwater/glycol mixtures. Examples of suitable gels include water gelatingels, hydrogels, water/methyl cellulose gels and gels comprised ofcopolymer rubber based materials such a styrene-butadiene-styrene rubberand paraffinic and/or naphthenic oil. Examples of suitable melts includewaxes and hot melts. Hot-melts are materials which at or about normalroom temperatures are solid but at elevated temperatures become liquid.A high melting temperature is desirable since the liquid core is heatedto high temperatures during the molding of the inner core, outer core,and the cover. The liquid can be a reactive liquid system, whichcombines to form a solid. Examples of suitable reactive liquids aresilicate gels, agar gels, peroxide cured polyester resins, two partepoxy resin systems and peroxide cured liquid polybutadiene rubbercompositions.

The “effective compression constant,” which is designated EC, is theratio of deflection of a 1.50 inch diameter sphere made of any singlematerial used in the core under a 100 kg load that as represented by theformula EC=F/d, where, F is a 100 kg load; and d is the deflection inmillimeters. If the sphere tested is only inner core material, theeffective compression constant for the inner core material alone isdesignated EC_(IC). If the sphere tested is only outer core material,the effective compression constant for the outer core material alone isdesignated EC_(OC). The sum of the constants for the inner core EC_(IC)and outer core EC_(OC) is the constant EC_(S). If the sphere tested isinner and outer core material, the core effective compression constantis designated EC_(C). It is has been determined that very favorablecores are formed when their core effective compression constant EC_(C)is less than the sum of the effective compression constants of the innercore and outer core EC_(S). It is recommended that the core effectivecompression constant EC_(C) is less than about 90% of the sum of theeffective compression constants of the inner core and outer core EC_(S).More preferably, the core effective compression constant EC_(C) is lessthan or equal to about 50% of the sum of the effective compressionconstants of the inner core and outer core EC_(S). The ratios of theinner core material to outer core material and the geometry of the innercore to the outer core are selected to achieve these core effectivecompression constants.

The resultant golf balls typically have a coefficient of restitution ofgreater than about 0.7, preferably greater than about 0.75, and morepreferably greater than about 0.78. The golf balls also typically havean Atti compression of at least about 40, preferably from about 50 to120, and more preferably from about 60 to 100. The golf ball curedpolybutadiene material typically has a hardness of at least about 15Shore A, preferably between about 30 Shore A and 80 Shore D, morepreferably between about 50 Shore A and 60 Shore D.

In addition to the HNP's neutralized with organic fatty acids and saltsthereof, core compositions may comprise at least one rubber materialhaving a resilience index of at least about 40. Preferably theresilience index is at least about 50. Polymers that produce resilientgolf balls and, therefore, are suitable for the present invention,include but are not limited to CB23, CB22, commercially available fromof Bayer Corp. of Orange, Tex., BR60, commercially available fromEnichem of Italy, and 1207G, commercially available from Goodyear Corp.of Akron, Ohio.

Additionally, the unvulcanized rubber, such as polybutadiene, in golfballs prepared according to the invention typically has a Mooneyviscosity of between about 40 and about 80, more preferably, betweenabout 45 and about 65, and most preferably, between about 45 and about55. Mooney viscosity is typically measured according to ASTM-D1646.

When golf balls are prepared according to the invention, they typicallywill have dimple coverage greater than about 60 percent, preferablygreater than about 65 percent, and more preferably greater than about 75percent. The flexural modulus of the cover on the golf balls, asmeasured by ASTM method D6272-98, Procedure B, is typically greater thanabout 500 psi, and is preferably from about 500 psi to 150,000 psi. Asdiscussed herein, the outer cover layer is preferably formed from arelatively soft polyurethane material. In particular, the material ofthe outer cover layer should have a material hardness, as measured byASTM-D2240, less than about 45 Shore D, preferably less than about 40Shore D, more preferably between about 25 and about 40 Shore D, and mostpreferably between about 30 and about 40 Shore D. The casing preferablyhas a material hardness of less than about 70 Shore D, more preferablybetween about 30 and about 70 Shore D, and most preferably, betweenabout 50 and about 65 Shore D.

In a preferred embodiment, the intermediate layer material hardness isbetween about 40 and about 70 Shore D and the outer cover layer materialhardness is less than about 40 Shore D. In a more preferred embodiment,a ratio of the intermediate layer material hardness to the outer coverlayer material hardness is greater than 1.5.

It should be understood, especially to one of ordinary skill in the art,that there is a fundamental difference between “material hardness” and“hardness, as measured directly on a golf ball.” Material hardness isdefined by the procedure set forth in ASTM-D2240 and generally involvesmeasuring the hardness of a flat “slab” or “button” formed of thematerial of which the hardness is to be measured. Hardness, whenmeasured directly on a golf ball (or other spherical surface) is acompletely different measurement and, therefore, results in a differenthardness value. This difference results from a number of factorsincluding, but not limited to, ball construction (i.e., core type,number of core and/or cover layers, etc.), ball (or sphere) diameter,and the material composition of adjacent layers. It should also beunderstood that the two measurement techniques are not linearly relatedand, therefore, one hardness value cannot easily be correlated to theother.

In one embodiment, the core of the present invention has an Atticompression of between about 50 and about 90, more preferably, betweenabout 60 and about 85, and most preferably, between about 65 and about85. The overall outer diameter (“OD”) of the core is less than about1.590 inches, preferably, no greater than 1.580 inches, more preferablybetween about 1.540 inches and about 1.580 inches, and most preferablybetween about 1.525 inches to about 1.570 inches. The OD of the casingof the golf balls of the present invention is preferably between 1.580inches and about 1.640 inches, more preferably between about 1.590inches to about 1.630 inches, and most preferably between about 1.600inches to about 1.630 inches.

The present multilayer golf ball can have an overall diameter of anysize. Although the United States Golf Association (“USGA”)specifications limit the minimum size of a competition golf ball to1.680 inches. There is no specification as to the maximum diameter. Golfballs of any size, however, can be used for recreational play. Thepreferred diameter of the present golf balls is from about 1.680 inchesto about 1.800 inches. The more preferred diameter is from about 1.680inches to about 1.760 inches. The most preferred diameter is about 1.680inches to about 1.740 inches.

The golf balls of the present invention should have a moment of inertia(“MOI”) of less than about 85 and, preferably, less than about 83. TheMOI is typically measured on model number MOI-005-104 Moment of InertiaInstrument manufactured by Inertia Dynamics of Collinsville, Conn. Theinstrument is plugged into a PC for communication via a COMM port and isdriven by MOI Instrument Software version #1.2.

U.S. Pat. Nos. 6,193,619; 6,207,784; and 6,221,960, and U.S. applicationSer. No. 09/594,031, filed Jun. 15, 2000; Ser. No. 09/677,871, filedOct. 3, 2000, and Ser. No. 09/447,652, filed Nov. 23, 1999, areincorporated in their entirety herein by express reference thereto.

The highly-neutralized polymers of the present invention may also beused in golf equipment, in particular, inserts for golf clubs, such asputters, irons, and woods, and in golf shoes and components thereof.

Other than in the operating examples, or unless otherwise expresslyspecified, all of the numerical ranges, amounts, values and percentagessuch as those for amounts of materials, and others in the specificationmay be read as if prefaced by the word “about” even though the term“about” may not expressly appear with the value, amount or range.Accordingly, unless indicated to the contrary, the numerical parametersset forth in the specification and attached claims are approximationsthat may vary depending upon the desired properties sought to beobtained by the present invention. At the very least, and not as anattempt to limit the application of the doctrine of equivalents to thescope of the claims, each numerical parameter should at least beconstrued in light of the number of reported significant digits and byapplying ordinary rounding techniques.

Notwithstanding that the numerical ranges and parameters setting forththe broad scope of the invention are approximations, the numericalvalues set forth in the specific examples are reported as precisely aspossible. Any numerical value, however, inherently contain certainerrors necessarily resulting from the standard deviation found in theirrespective testing measurements. Furthermore, when numerical ranges ofvarying scope are set forth herein, it is contemplated that anycombination of these values inclusive of the recited values may be used.

The invention described and claimed herein is not to be limited in scopeby the specific embodiments herein disclosed, since these embodimentsare intended solely as illustrations of several aspects of theinvention. Any equivalent embodiments are intended to be within thescope of this invention. Indeed, various modifications of the inventionin addition to those shown and described herein will become apparent tothose skilled in the art from the foregoing description. Suchmodifications are also intended to fall within the scope of the appendedclaims.

1. A golf ball comprising: a core comprising: a first polymer comprisingan acid group fully-neutralized by a salt of an organic acid or asuitable base of the organic acid and a sufficient cation source toneutralize the acid groups 100%; and a nano-material having an averageparticle size of 100 nm or less, present in an amount sufficient toadjust at least one material property of the first polymer by 5% to 50%when compared to the material property of the first polymer comprising amaterial identical to the nano-material but having an average particlesize greater than 1000 nm; a cover layer; and an intermediate layerdisposed between the core and the cover layer, the intermediate layercomprising a second polymer comprising an acid group fully-neutralizedby a salt of an organic acid or a suitable base of the organic acid anda sufficient cation source to neutralize the acid groups 100%; whereinthe core has a compression of greater than 90 and up to and including120 and a diameter of between 1.58 inches and 1.64 inches.
 2. The golfball of claim 1, wherein the material property is selected from thegroup consisting of density, hardness, moment of inertia, flexuralmodulus, stiffness modulus, abrasion resistance, heat resistance, impactresistance, water vapor transmission rate, and resilience.
 3. The golfball of claim 1, wherein the material property of the first polymer isflexural modulus at least 10% to 50% greater than when compared to theflexural modulus of the polymer comprising a material identical to thenano-material and having an average particle size greater than 1000 nm.4. The golf ball of claim 1, wherein the material property of the firstpolymer is hardness at least 5% to 25% greater than when compared to thehardness of the polymer comprising a material identical to thenano-material, the material having an average particle size greater than1000 nm.
 5. The golf ball of claim 1, wherein the cover layer comprisesa polymer selected from the group consisting of ionomeric copolymers andterpolymers, ionomer precursors, thermoplastics, thermoplasticelastomers, polybutadiene rubber, balata, grafted metallocene-catalyzedpolymers, non-grafted metallocene-catalyzed polymers, single-sitepolymers, high-crystalline acid polymers and their ionomers,rosin-modified ionomers, bimodal ionomers, cationic ionomers, anionicionomers, polyurethanes, and polyureas.
 6. The golf ball of claim 1,wherein the intermediate layer comprises the nano-material having aparticle size of 100 nm or less, present in an amount sufficient toadjust at least one material property of the first polymer by 5% to 50%when compared to the material property of the first polymer comprising amaterial identical to the nano-material but having a particle sizegreater than 1000 nm.
 7. The golf ball of claim 1, wherein thenano-material comprise swellable layered materials; micaceous minerals;smectite minerals; carbon nanotubes; fullerenes; nanoscale titaniumoxides; iron oxides; ceramics; modified ceramics; metal and oxidepowders; titanium dioxide particles; single-wall and multi-wall carbonnanotubes; polymer nanofibers; carbon nanofibrils; nitrides; carbides;sulfides; ormocers; glass ionomers; resin-modified glass ionomers;silicon ionomers; polymerizable cements; metal-oxide polymer composites;lipid-based nanotubules, graphite sheets, or polyhedral oligomericsilsequioxanes.
 8. The golf ball of claim 7, wherein the swellablelayered material sufficiently sorbs an intercalant polymer to increasethe interlayer spacing between adjacent nano-materials to at least about10 Å.
 9. The golf ball of claim 7, wherein the swellable layeredmaterials comprise phyllosilicates, montmorillonite, sodiummontmorillonite; magnesium montmorillonite; calcium montmorillonite;nontronite; beidellite; volkonskoite; hectorite; saponite; sauconite;sobockite; stevensite; svinfordite; or vermiculite.
 10. The golf ball ofclaim 9, wherein the swellable layered material comprisesphyllosilicates having a negative charge ranging from about 0.15 toabout 0.9 charges per formula unit and a commensurate number ofexchangeable metal cations.
 11. The golf ball of claim 1, wherein thenano-materials are chemically-modified.
 12. The golf ball of claim 1,wherein the cover layer consisting essentially of a polyurethane, apolyurea, a polyurea-urethane, or a polyurethane-urea.
 13. The golf ballof claim 1, wherein a water vapor barrier layer is disposed between thecover and the core.
 14. The golf ball of claim 13, wherein the watervapor barrier layer has a vapor transmission rate of less than 0.45g-mm²-day.
 15. The golf ball of claim 1, wherein the cover comprises acastable polyurea material.